WO2021055388A1 - 2,5-dimercapto-1,3,4-thiadiazole ("dmtd") derivatives - Google Patents

2,5-dimercapto-1,3,4-thiadiazole ("dmtd") derivatives Download PDF

Info

Publication number
WO2021055388A1
WO2021055388A1 PCT/US2020/050947 US2020050947W WO2021055388A1 WO 2021055388 A1 WO2021055388 A1 WO 2021055388A1 US 2020050947 W US2020050947 W US 2020050947W WO 2021055388 A1 WO2021055388 A1 WO 2021055388A1
Authority
WO
WIPO (PCT)
Prior art keywords
dmtd
group
formula
derivative
consists essentially
Prior art date
Application number
PCT/US2020/050947
Other languages
French (fr)
Inventor
Paul E. Adams
Christopher M. RASIK
Ryan KONRAD
Original Assignee
The Lubrizol Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Lubrizol Corporation filed Critical The Lubrizol Corporation
Priority to US17/760,830 priority Critical patent/US20220380326A1/en
Priority to EP20780882.5A priority patent/EP4031537A1/en
Priority to CA3150299A priority patent/CA3150299A1/en
Priority to CN202080064720.8A priority patent/CN114401949A/en
Publication of WO2021055388A1 publication Critical patent/WO2021055388A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • DMTD 2,5-DIMERCAPTO-1,3,4-THIADIAZOLE
  • DMTD DERIVATIVES BACKGROUND OF THE INVENTION
  • the disclosed technology relates to derivatives of 2,5-dimercapto-1,3,4-thi- adiazole.
  • Some simple alkyl and aryl substituted DMTD derivatives are known, for example, as taught in US 2,736,729, granted Feb. 28, 1956 to Krzikalla et al. and US3,212,892, granted Oct.19, 1965, to von König et al..
  • Simple acrylic acid alkyl and aryl esters of DMTD are also known, for example, as taught in JP 2013234126, pub- lished Nov.21, 2013 to Oya et al., and US 5,258,395, granted Nov.2, 1993 to Murase et al..
  • New chemistries are needed that can readily change oxidation states and are based on organic chemistry. Examples of such chemistry in the art usually start with some or all of relatively expensive starting materials and reagents, may need multiple steps to obtain the target final product, generate large quantities of undesir- able process wastes, and could also require tedious purification steps.
  • the disclosed technology therefore, solves the problem of difficult to pro- cute and expensive but readily oxidizable organic chemistry by providing new DMTD derivatives that are synthesized in only one or two steps, starting from readily avail- able and inexpensive raw materials, use processing that generates little or no waste, and involve reactions which proceed rapidly and in high product conversions.
  • DMTD derivative obtained as the reaction product of: a) 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b) at least one of a: i) halo-ether group, ii) a halo-alcohol group, iii) an epoxide group, iv) a carboxamide group, and v) carboxylate group.
  • DMTD derivatives can be further reacted with a base.
  • any of the foregoing DMTD derivatives can be further reacted with an oxidizing reagent.
  • the foregoing reaction products can include a mono-ether DMTD deriva- tive, in a salt form or not, or as a sulfur coupled bis-compound.
  • the foregoing reaction products can include a mono-alcohol DMTD deriv- ative, in a salt form or not, or as a sulfur coupled bis-compound.
  • the foregoing reaction products can include a mono-carboxamide DMTD derivative, in a salt form or not, or as a sulfur coupled bis-compound.
  • the foregoing reaction products can include a mono-carboxylate DMTD de- rivative, in a salt form or not, or as a sulfur coupled bis-compound.
  • Another aspect of the technology is directed to a DMTD derivative obtained as the reaction product of: a) 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b) at least one of a: i) a halogenated hydrocarbyl group, and ii) (meth)acrylate group, and c) an oxidizing agent.
  • DMTD 2,5-dimercapto-1,3,4-thiadiazole
  • the foregoing reaction products can include a mono-alkyl bis-DMTD de- rivative.
  • the foregoing reaction products can also include a mono-(meth)acrylate bis- DMTD derivative.
  • Another aspect of the technology is directed to a zwitterionic DMTD derivative obtained as the reaction product of: a) 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b) at least one of: i) a linear, branched, saturated or unsaturated, cyclic halogenated C 1 to C 22 alkyl or aryl quaternary ammonium group, ii) a quaternary ammonium con- taining halo-ether group, iii) a quaternary ammonium containing halo-alcohol group, iv) a quaternary ammonium containing epoxide group, v) a quaternary ammonium containing carboxylate group, and vi) a quaternary ammonium containing carbox- amide group, and c) a strong base.
  • DMTD 2,5-dimercapto-1,3,4-thiadiazole
  • the foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing alkyl DMTD derivative. [0015] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing ether DMTD derivative. [0016] The foregoing reaction products can also include a zwitterionic mono- qua- ternary ammonium containing alcohol DMTD derivative. [0017] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing (meth)acrylamide DMTD derivative.
  • reaction products can include a zwitterionic mono- quater- nary ammonium containing (meth)acrylate DMTD derivative.
  • DETAILED DESCRIPTION OF THE INVENTION [0019] Various preferred features and embodiments will be described below by way of non-limiting illustration.
  • DMTD derivatives include reaction products of DMTD and other chemical reagents via a variety of different chemical reactions.
  • the DMTD derivatives can be represented in the pure form by formula I: Formula I where each “X” individually, is an alkali or alkaline earth metal, such as Li, Na, K, Mg, or Ca, a trialkyl amine, or a quaternary amine (including for purposes of this disclosure, ammonia), or H; “m” is 1, 2 or 3, and “n” is 1 or 2; and where “Y” is: “[RO] o R,” where “o” is an integer from 1 to 100; “R[OH] p A,” where “p” is an integer from 1 to 6 and “A” is H or an amine, such as a trialkyl amine or a quaternary amine salt; a carboxamide, such as a (meth)acrylamide of “CH 2 CH[CH 3 or H]C(O)NHZ,” where “Z” is H
  • R group can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, including branched versions thereof, such as, for example, isobutyl, ethylhexyl, isoamyl, and the like, as well as aromatic groups (e.g. benzyl, phenyl, tolyl, xylyl, naphthyl, etc.) or cyclic groups (e.g., cyclohexyl).
  • a base may be employed.
  • Such a base may be, for example, an alkaline or alkaline earth metal hydroxide or carbonate, or an amine, such as, for example a trialkyl amine.
  • “X” in the foregoing formulas can be an alkali or alkaline earth metal such as Li, Na, K, Mg, or Ca, or a trialkyl amine. If a base is not employed, “X” would be H and the positive and negative charges associated therewith would be absent. [0024] In its un-coupled form, m and n in Formula I would both be 1, as shown in Formula II below.
  • reaction products can also be further reacted with an oxidizing agent, such as, for example, hydrogen peroxide, to form a sulfur coupled “bis-” form of the particular derivative.
  • an oxidizing agent such as, for example, hydrogen peroxide
  • n in Formula I would be 2
  • m could be 1, 2 or 3
  • X and the positive and negative charges associated therewith would be absent.
  • Such coupled DMTD derivatives can be prepared by preparing the un-coupled compound and then introducing an oxidizing reagent, such as hydrogen peroxide or others, as would be known by those of ordinary skill in the art. Examples of coupled DMTD derivative are shown in Formulas III, IV and V below.
  • the DMTD derivatives can be the reaction product resulting from the displacement using electron deficient hydrocarbons be- tween DMTD and a halogenated ether (“halo-ether”) group (which include simple ethers as well as polyethers).
  • halo-ether halogenated ether
  • the foregoing reaction product can further be reacted in an acid-base reaction with a base to form a salt or an oxidizing agent to form a bis- compound.
  • group for example as in a halogenated alkyl or aryl group, halo-ether group, halo-alcohol group, (meth)acrylate group, and (meth)acrylamide group, depending on the context, refers to the structure of the stated group on its own or as the structure in which the group would form after reaction with another compound.
  • the substituent Y of the DMTD derivatives of Formula I would be “[RO] o R,” with R and o as defined above.
  • the mono-ether DMTD derivatives may be represented by formula VI: Formula VI where X, R, m, and n are as set forth for Formula I, and “o” is an integer from 1 to 100, or 1 to 75, or 1 to 50, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 2 to 10 or 4 to 10 or 6 to 10. [0030] Where the mono-ether DMTD derivative is not reacted with a base, the mono-ether DMTD derivative would be represented by: . [0031] Where the mono-ether DMTD derivative is reacted with a base, the mono-ether DMTD derivative would be represented by: .
  • Example simple ethers i.e., the [RO] o R group where o is 1) that may be employed include dimethyl ether (both R’s are methyl groups, o is 1), diethyl ether (both R’s are ethyl groups, o is 1), dipropyl ether (both R’s are propyl groups, o is 1), methyl ethyl ether (one R is a methyl group, one R is an ethyl group, o is 1), methyl phenyl ether (one R is a methyl group, one R is n phenyl group, o is 1).
  • Example polyethers i.e., the [RO] o R group where o is 2 to 100
  • paraformaldehyde i.e., the [RO] o R group where the repeating R is a methyl group and the non-repeating R is H, o is 8 to 100
  • polyethylene glycol i.e., the [RO] o R group where the repeating R is an ethyl group and the non-repeating R is H, o is 2 to 100
  • polypropylene glycol i.e., the [RO] o R group where the repeat- ing R is an iso-propyl group and the non-repeating R is H, o is 2 to 100
  • polytetra- hydrofuran i.e., the [RO] o R group where the repeating R is a butyl group and the non-repeating R is H, o is 2 to 100).
  • DMTD can be reacted with a halomethyl ether, and optionally a base and/or oxidizing reagent, to provide a mono-ether DMTD de- rivative of one or more of formula VI(1), (2), (3), or (4).
  • DMTD can be reacted with a polyeth- ylene glycol halide, and optionally a base and/or oxidizing reagent, to provide a mono-ether DMTD derivative of one or more of formula VI(5), (6), (7), or (8):
  • the DMTD derivatives can be the reaction product resulting from the displacement using electron deficient hydrocarbons between DMTD and a halogenated alcohol (“halo-alcohol”) group. Similar DMTD derivatives can be pre- pared from an epoxide opening reaction between DMTD and an epoxide group. The foregoing reaction products can further be reacted in an acid-base reaction with a base to form a salt, or an oxidizing agent to form a bis- compound.
  • halo-alcohol halogenated alcohol
  • the sub- stituent Y of the DMTD derivatives of Formula I would be “R[OH] p A,” and R, p and A as defined above.
  • the mono-alcohol DMTD derivatives may be represented by formula VII: Formula VII where X, R, m, and n are as set forth for Formula I, and “p” is an integer from 1 to 6 and “A” is H or an amine, such as a trialkyl amine or a quaternary amine salt.
  • the mono-alcohol DMTD derivative is not reacted with a base
  • the mono-alco- hol DMTD derivative would be represented by: .
  • the mono-alcohol DMTD derivative is reacted with a base
  • the mono-alcohol DMTD derivative would be represented by: .
  • the mono-alcohol DMTD derivative is reacted with an oxidizing reagent
  • the mono-alcohol DMTD derivative would be represented by: .
  • Example mono-alcohols include propanol (i.e., R is a linear or branched propyl group) which would be ob- tained, for example, from a halogenated propanol, such as chloropropanol or propyl- ene oxide; hexanol (i.e., R is a linear or branched hexyl group) which would be ob- tained, for example, from a halogenated hexanol, such as chlorohexanol; butanol (i.e., R is a linear or branched butyl group) which would be obtained, for example, from a halogenated butanol, such as chlorobutanol or butylene oxide; phenyl propanol (i.e., R is propyl or ethylbenzene
  • propanol i.e., R is a linear or branched propyl group
  • Example polyols i.e., the R[OH] p A group where p is 2 to 6 and A is H
  • sugar alcohols polyvinyl alcohols
  • ethylene glycol i.e., R is an ethyl group, p is 2)
  • propylene glycol i.e., R is a linear or branched propyl group, p is 2)
  • butanediol i.e., R is a linear or branched butyl group, p is 2)
  • glycerol i.e., R is a butyl group, p is 3
  • Example alcohol amines i.e., the R[OH] p A group where A is an amine
  • R[OH] p A group where A is an amine examples include ethanolamine (i.e., R is an ethyl group, p is 1, A is NH 2 ), propanolamine (i.e., R is a propyl group, p is 1, A is NH 2 ), propanol dimethyl- amine (i.e., R is a propyl group, p is 1, A is N(CH 3 ) 2 ), propanol quaternary amine halide salt (i.e., R is a propyl group, p is 1, A is a N + (CH 3 ) 3 •Cl-).
  • ethanolamine i.e., R is an ethyl group, p is 1, A is NH 2
  • propanolamine i.e., R is a propyl group, p is 1, A is NH
  • DMTD can be reacted with a glycidol, and optionally a base and/or oxidizing reagent, to provide a mono-alcohol derivative of one or more of formula VII(1), (2), (3), or (4).
  • DMTD can be reacted with a glycidol methacrylate, and optionally a base and/or oxidizing reagent, to provide a mono-al- cohol derivative of one or more of formula VII(5), (6), (7), or (8).
  • DMTD can be reacted with a 2- epoxy quaternary ethyl amine halide, and optionally a base and/or oxidizing reagent, to provide a mono-alcohol derivative of one or more of formula VII(9), (10), (11), or (12).
  • the DMTD derivatives can also be the reaction product resulting from a 1,4 addition between DMTD and a carboxamide group capable of 1,4 addition.
  • the foregoing reaction product can further be reacted in an acid-base reaction with a base to form a salt or an oxidizing agent to form a bis- compound.
  • Carboxamide groups capable of 1,4 addition can be readily envisaged by those of skill in the art, and include, both mono-carboxamides and di-carboxamides.
  • Example carboxamides can include, but not be limited to, itaconic amide, citraconic amide, maleic amide, fumaric amide, mesaconic amide, as well as (meth)acrylamide.
  • the carboxamides can be primary, or can be substituted with one or more “R” groups to form a secondary or tertiary amide group.
  • R tertiary amide group.
  • (meth)acrylate can refer to both acrylate and methacrylate
  • (meth)acrylamide includes both acrylamide and methacrylamide.
  • carboxamide containing DMTD derivatives can result from 1,4 addition between DMTD and a (meth)acrylamide group, wherein the substituent Y of the DMTD derivatives of Formula I would be “CH 2 CH[CH 3 or H]C(O)NHZ,” and Z is as defined above.
  • Such mono-(meth)acrylamide DMTD de- rivatives may be represented by formula VIII: Formula VIII where X, m, and n are as set forth for Formula I, and “Z” is H, “R,” RSO 3 -Na + , RSO 3 H, or RN + (R) 3 Cl-.
  • the mono-ether DMTD derivative would be represented by: .
  • the mono-(meth)acrylamide DMTD derivative is reacted with a base
  • the mono-ether DMTD derivative would be represented by: .
  • the mono-(meth)acrylamide DMTD derivative is reacted with an oxidizing reagent
  • the mono-ether DMTD derivative would be represented by:
  • DMTD can be reacted with methacrylaminopropyl trimethyl ammonium chloride to provide a mono-methacrylamide DMTD derivative of Formula VIII, in either coupled or un-coupled form, where Z (CH 2 ) 3 N + (CH 3 ) 3 Cl-, m is 1, 2 or 3 and n is 1 or 2 and X is an optional alkali or alkaline earth metal or amine.
  • DMTD can be reacted with 2-acrylamino-2- methylpropane sulfonic acid to provide a DMTD derivative of Formula VIII, in either coupled or un-coupled form, where Z is C(CH 3 ) 2 CH 2 SO 3 H, m is 1, 2 or 3 and n is 1 or 2 and X is an optional alkali or alkaline earth metal or amine.
  • DMTD can be reacted with 2-acrylamino-2- methylpropane sulfonic acid sodium salt to provide a DMTD derivative of Formula VIII, in either coupled or un-coupled form, where Z is C(CH 3 ) 2 CH 2 SO 3 -Na + , m is 1, 2 or 3 and n is 1 or 2 and X is an optional alkali or alkaline earth metal or amine.
  • the DMTD derivatives can also be the reaction product resulting from a 1,4 addition between DMTD and a carboxylate group capable of 1,4 addition.
  • Carboxylate groups capable of 1,4 addition can be readily envisaged by those of skill in the art, and include, both mono-carboxylates and di-carboxylates as well as higher carboxylates, e.g., tricarboxylates, tetracarboxylates, etc.
  • Example car- boxylates can include, but not be limited to, itaconates, citraconates, maleates, fumarates, mesaconates, as well as (meth)acrylates.
  • the carboxylates can be in the form of a salt with an alkali or alkaline earth metal, an ammonia group, or an ester with an “R” group.
  • the salt can be obtained by 1,4 addition of the salted monomer, or by addition of the ester followed by saponification with an alkali or alkaline earth metal hydroxide or ammonium hydroxide.
  • the carboxylate does not include a (meth)acrylic acid or a (meth)acrylate where the ester group of the (meth)acrylate is a simple R group.
  • the carboxylate containing DMTD derivatives can result from 1,4 addition between DMTD and a carboxylic acid or carboxylate.
  • DMTD may be reacted with aconitic acid to form a DMTD derivative with an aconitic acid connected off of a substituent sulfur, followed by reaction with an alkali metal hydroxide, alkali earth metal hydroxide, or ammonium hydroxide.
  • a further example could be a carboxylate containing DMTD derivative re- sulting from the 1,4 addition between DMTD and a dialkyl itaconate, such as dime- thyl itaconate, wherein the substituent Y of the DMTD derivatives of Formula I would be dimethyl itaconate, for example, as represented by formula
  • the carboxylate could also be, for example, a di- alkali or dialkaline earth itaconate salt, such disodium itaconate, represented, for ex- ample, by formula .
  • Another example carboxylate containing DMTD derivative can result from 1,4 addition between DMTD and a dialkyl maleate, such as dimethyl maleate, wherein the substituent Y of the DMTD derivatives of Formula I would be dimethyl maleate, for example, as represented by formula
  • the carboxylate could also be, for example, a di- alkali or dialkaline earth maleate salt, such disodium maleate, represented, for exam- ple, by formula .
  • Further examples can include, for example, the reaction of methyl acrylate and DMTD, or dimethyl maleate and DMTD.
  • these exam- ples can also include, for example, the reaction of sodium acrylate or disodium maleate, or the foregoing esters could be saponified in the presence of sodium hydroxide to obtain the salts.
  • a carboxylate containing DMTD derivatives can result from 1,4 addition between DMTD and a (meth)acrylate group in which the ester group is a quaternary ammonium group or a sulfur trioxide containing group, wherein the substituent Y of the DMTD derivatives of Formula I would be “CH 2 CH[CH 3 or H]C(O)OZ.”
  • the mono-(meth)acrylate DMTD derivatives may be represented by formula IX: Formula IX where X, m, and n are as set forth for Formula I, and “Z” is X, RSO 3 -Na + , RSO 3 H, RN + (R) 3 SO 3 -, RN + (R) 3 SO 3 -K + , RSO 3 -NH 4 + or RN + (R) 3 Cl-.
  • the mono-ether DMTD derivative would be represented by: where Z is X, RSO 3 -Na + , RSO 3 H, RN + (R) 3 SO 3 -, RN + (R) 3 SO 3 -K + , RSO 3 -NH 4 + or RN + (R) 3 Cl-.
  • the mono-ether DMTD derivative would be represented by: where Z is X, RSO 3 -Na + , RSO 3 H, RN + (R) 3 SO 3 -, RN + (R) 3 SO 3 -K + , RSO 3 -NH 4 + or RN + (R) 3 Cl-.
  • Z is X, RSO 3 -Na + , RSO 3 H, RN + (R) 3 SO 3 -, RN + (R) 3 SO 3 -K + , RSO 3 -NH 4 + or RN + (R) 3 Cl-.
  • DMTD can be reacted with methacryloxyethyl trimethyl ammonium chloride to provide a mono-methacrylate DMTD derivative of Formula IX, in either coupled or un-coupled form, where Z is (CH 2 ) 2 N + (CH 3 ) 3 Cl-, m is 1, 2 or 3 and n is 1 or 2 and X is an optional alkali or alkaline earth metal or amine.
  • the DMTD derivatives can also be the reaction product resulting from a 1,4 addition between DMTD and a (meth)acrylate group and an oxidizing agent to form a bis- compound.
  • the sub- stituent Y of the DMTD derivatives of Formula I would be “CH 2 CH[CH 3 or H]C(O)OZ,” and Z is R or H.
  • the mono-(meth)acrylate DMTD derivatives may be represented by formula X: Formula X where m is 1, 2 or 3 and “Z” is R or H.
  • DMTD can be reacted with methyl acrylate, followed by an oxidizing agent to provide mono-acrylate bis-DMTD derivative of Formula X, where Z is CH 3 , and m is 1, 2 or 3.
  • DMTD can be reacted with 2-ethylhexyl acrylate, followed by an oxidizing agent, to provide a mono-acrylate bis-DMTD de- rivative of Formula X where Z is a 2-ethylhexyl group, and m is 1, 2 or 3.
  • the DMTD derivatives can also be the reaction product resulting from the displacement using electron deficient hydrocarbons between DMTD and a halogen- ated hydrocarbyl (“halo-hydrocarbyl”) group (which include linear, branched, satu- rated or unsaturated, or cyclic alkyl group, or aryl group, where an unsaturated alkyl group is synonymous with an alkene), and further reacted with an oxidizing agent to form a bis- compound.
  • halo-hydrocarbyl which include linear, branched, satu- rated or unsaturated, or cyclic alkyl group, or aryl group, where an unsaturated alkyl group is synonymous with an alkene
  • the substituent Y of the DMTD derivatives of Formula I would be “R,” as defined above, n would be 2 and m would be 1, 2 or 3.
  • the substituent may be any hydrocarbyl group, the derivative is collectively referred to herein and in the claims as a “mono- alkylated” DMTD derivative.
  • the mono-alkylated bis-DMTD derivatives may be represented by formu- las XI: Formula XI where m is 1, 2 or 3, and R is a linear, branched, saturated or unsaturated, cyclic C 1 to C 12 , or C 1 to C 10 , or C 1 to C 8 , or even C 1 to C 6 alkyl or aryl group; or H.
  • DMTD can be reacted with a benzylhalide and an oxidizing reagent, to provide a mono-arylated DMTD derivative of one or more of formula XI(1), (2), or (3).
  • DMTD derivatives such as those discussed above may include a quaternary ammonium substituent and be treated with a strong base, such as LiOH, NaOH, KOH, Ca(OH) 2 , a quaternary amine such as R 4 NOH, and the like to produce a zwitterionic species.
  • a strong base such as LiOH, NaOH, KOH, Ca(OH) 2
  • a quaternary amine such as R 4 NOH
  • the foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing alkyl DMTD derivative represented as shown in formula XII: [0081]
  • the foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing ether DMTD derivative represented as shown in formula XIII: [0082]
  • the foregoing reaction products can also include a zwitterionic mono- qua- ternary ammonium containing alcohol DMTD derivative represented as shown in for- mula XIV: [0083]
  • the foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing carboxamide, such as, for example, a (meth)acrylamide DMTD derivative represented as shown in formula XV: Formula XV [0084]
  • the foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing
  • DMTD can be reacted with methacrylaminopropyl trimethyl ammonium chloride to provide a mono-methacrylamide DMTD derivative of For- mula XV where Z (CH 2 ) 3 N + (CH 3 ) 3 Cl-, m is 1, 2 or 3 and n is 1 or 2, followed by treatment with NaOH to afford a zwitterion of formula XV’: Formula XV’ .
  • the amount of each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial ma- terial, that is, on an active chemical basis, unless otherwise indicated.
  • Example 2 Synthesis of 2-(2-Ethoxyethoxycarboxyethyl)thio-5-thiol- 1,3,4-Thiadiazole 150.2 grams of DMTD, 150 grams of toluene solvent, and 188.2 grams of 2-ethoxyethoxy acrylate were added to a 1-liter flask and heated at 85 oC for two hours. Toluene solvent was vacuum stripped on a rotary evaporator at 3 mm Hg vacuum and 80 oC for four hours.
  • Example 3 Synthesis of 2-(Methacryloylaminopropyltrimethylammo- nium chloride)thio-5-thiol-1,3,4-Thiadiazole. 84.1 grams of DMTD, 247 grams of 50% aqueous Methacryloylaminopropyltrimethylammonium chloride, 0.42 gram of sodium hydroxide, and 300 grams of water were added to a one liter flask and heated under nitrogen at 90 oC for 8 hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 oC oven on standing, followed by vacuum drying at 2 mm Hg and 95 oC for 20 hours.
  • Example 4 Synthesis of 2-(Methacryloylaminopropyltrimethylammo- nium)thio-5-thiolate-1,3,4-Thiadiazole. 122.7 grams of 2-(Methacry- loylaminopropyltrimethylammonium chloride) thio-5-thiol-1,3,4-Thiadiazole, 13.2 grams of sodium hydroxide, and 200 grams of deionized water were added to a one liter flask and heated under nitrogen at 70 oC for three hours.
  • Example 8 72.7 grams of 2-(Acryloylamino-2- methylpropylsulfonic acid)-5-thiol-1,3,4-thiadiazole prepared in Example 16, 16.25 grams of sodium hydroxide, 200 grams of deionized water solvent were added to a one liter flask and heated under nitrogen at 85 oC for 3 hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 oC oven on standing, followed by vacuum drying at 3 mm Hg and 105 oC for 16 hours. The final product was a crystalline solid. [0094] Example 8.
  • Example 9 Synthesis of 2-(2-hydroxypropyltrimethylammonium chlo- ride)thio-5-thiol-1,3,4-thiadiazole. 45.07 grams of DMTD, 45.9 grams of technical grade glycidyltrimethylammonium chloride, and 200 grams of reagent grade acetoni- trile solvent were added to a one liter flask and heated under nitrogen at 80 oC for 8 hours. The mixture was transferred to an open beaker and most of the solvent was evaporated in a 65 oC oven on standing, followed by vacuum drying at 3.5 mm Hg and 90 oC for 22 hours. The final product was a yellow crystalline solid. [0096] Example 10.
  • Example 11 Synthesis of Sodium 2-(n-Hexyl)thio-5-thiolate-1,3,4-Thi- adiazole. 42.5 grams of 2-(n-Hexyl)thio-5-thiol-1,3,4-Thiadiazole prepared in Ex- ample 24, 7.25 grams of sodium hydroxide, and 200 mL of toluene solvent were added to a 1-L flask and heated at reflux for 6 hours. Water distillate was collected using a Dean Stark trap.
  • Example 14 Synthesis of Potassium 2-[(Methacryloyloxy-3-sulfopro- pyl)thio-5-thiol-1,3,4-Thiadiazole. 73.9 grams of 3-sulfopropyl methacrylate potas- sium salt, 45.07 grams of DMTD, 0.2 gram of sodium hydroxide, and 250 grams of deionized water were added to a one liter flask and heated under nitrogen at 85-90 oC for 12 hours.
  • Example 15 Synthesis of Dipotassium 2-[(Methacryloyloxy-3-sul- fopropyl)thio-5-thiolate-1,3,4-Thiadiazole. 49.7 grams of 3-sulfopropyl methacry- late potassium salt, 38 grams of DMTD mono-potassium salt, 0.3 gram of potassium hydroxide, and 225 grams of deionized water were added to a one liter flask and heated under nitrogen at 85 oC for six hours.
  • Example 16 Synthesis of Dipotassium 2-(2-methylethyl-2-carbox- ylate)thio-5-thiolate-1,3,4-Thiadiazole. 100 grams of ester prepared in Example 23, 44.8 grams of potassium hydroxide, and 300 grams of deionized water were added to a one liter flask and heated at reflux (90 oC) for 14 hours while collecting distillate in a Dean Stark trap.
  • Example 17 Synthesis of Disodium 2-(Propyl-2,3-dicarbox- ylate)thio-5-thiol-1,3,4-Thiadiazole. 65.25 grams of Itaconic acid, 75.1 grams of DMTD, 0.3 gram of sodium hydroxide, and 200 grams of deionized water were added to a one liter flask and heated under nitrogen at 90 oC for six hours.
  • Example 18 Synthesis of Trisodium 2-(Propyl-2,3-dicarbox- ylate)thio-5-thiolate-1,3,4-Thiadiazole. 40 grams of DMTD mono-sodium salt, 30.2 grams of Itaconic acid, and 250 grams of deionized water were added to a one liter flask.
  • Example 19 Synthesis of Disodium 2-(Ethyl-2,3-dicarboxylate)thio- 5-thiol-1,3,4-Thiadiazole.
  • Example 20 46.45 grams of maleic acid, 60.1 grams of DMTD, 0.25 gram of sodium hydroxide, and 175 grams of deionized water were added to a one liter flask and heated under nitrogen at 90 oC for six hours. The clear mixture was cooled to room temperature and 32 grams of sodium hydroxide addded, followed by heating at 70 oC for four hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 oC oven on standing, followed by vacuum drying at 2 mm Hg and 95 oC for 24 hours. The product was obtained as a yellow solid. [0106] Example 20.
  • Example 21 Synthesis of 2-(2-Ethylhexylcarboxyethyl)thio-5-thiol-1,3,4- Thiadiazole. 150.2 grams of DMTD, 150 grams of toluene solvent, and 184.3 grams of 2- ethylhexyl acrylate were added to a 1-liter flask and heated at 85 oC for 7 hours. Toluene solvent was vacuum stripped on a rotary evaporator at 2 mm Hg vacuum and 80 oC for 5 hours to provide the desired product as a yellow liquid. [0108]
  • Example 22 Synthesis of 2-(Laurylcarboxy-2-methylethyl)thio-5-thiol- 1,3,4-Thiadiazole.
  • Example 25 After removal of the toluene on a rotary evaporator, the low-melting solid obtained was recrys- tallized from reagent grade toluene:n-hexane (80:20) wt.:wt. and dried in a vacuum oven to obtain the pure product.
  • Examples 25- 28 Using a similar procedure as Example 24 from the corre- sponding alkyl bromides, the following DMTD mono-alkylates were prepared: [0112]
  • Example 25 2-(2-Ethylhexyl)thio-5-thiol-1,3,4-Thiadiazole [0113]
  • Example 26 Example 26.
  • Example 27 2-Cyclohexylthio-5-thiol-1,3,4-Thiadiazole [0114]
  • Example 27 2-Isoamylthio-5-thiol-1,3,4-Thiadiazole [0115]
  • Example 28 2-(Ethylcarboxymethylene)thio-5-thiol-1,3,4-Thiadiazole [0116]
  • Example 29 Synthesis of 2-(2,3-Dicarboxypropyl)thio-5-thiol-1,3,4-Thiadi- azole.
  • Example 30 105.16g of 2,5-dimercapto-1,3,4-thiadiazole, 300g of deionized water, 91.1g of it- aconic acid and 0.3g of sodium hydroxide catalyst were added to a 1-L flask and heated under nitrogen at 88 oC for 10 hours and cooled. Most of the water was evaporated in a steam oven at 65 oC in an open beaker. The product was then dried in a vac oven at 95 oC until constant weight. The product yield was 194g. [0117] Examples 30-33. A procedure similar to Example 29 was used starting from acrylic acid, methacrylic acid, maleic acid, or aconitic acid to prepare the fol- lowing: [0118] Example 30.
  • Example 31 2-(2-Carboxyethyl)thio-5-thiol-1,3,4-thiadiazole [0119]
  • Example 31 2-(2-Methylethyl-2-carboxy)thio-5-thiol-1,3,4-thiadiazole [0120]
  • Example 32 2-(2,3-Dicarboxyethyl)thio-5-thiol-1,3,4-thiadiazole [0121]
  • Example 33 2-(2,3-Dicarboxyethyl)thio-5-thiol-1,3,4-thiadiazole [0121]
  • Example 34 (Alternate procedure for Example 18) Synthesis of Trisodium 2- (propyl-2,3-dicarboxylate)thio-5-thiolate-1,3,4-thiadiazole.
  • 32g of the diacid product pre- pared in Example 29, 250g of deionized water, and 13.7g of sodium hydroxide were added to a 1-L flask and heated under nitrogen at 85 oC for 6 hours. The mixture was transferred to an open beaker and most of the water evaporated in a steam oven at 65 oC.
  • Example 35 Dipotassium 2-(ethyl-2-carboxylate)thio-5-thiolate-1,3,4-thiadi- azole [0125]
  • Example 36 Tripotassium 2-(ethyl-1,2-dicarboxylate)thio-5-thiolate-1,3,4- thiadiazole [0126]
  • Example 37 Tripotassium 2-(ethyl-1,2-dicarboxylate)thio-5-thiolate-1,3,4- thiadiazole
  • Example 38 Tripotassium 2-(propyl-2,3-dicarboxylate)thio-5-thiolate-1,3,4- thiadiazole [0127]
  • Example 38 Dipotassium 2-(2-meth- ylethyl-2-carboxylate)thio-5-thiolate-1,3,4-thiadiazole [0128]
  • Example 39 (Alternate procedure for Example 20). Disodium 2-(2-meth- ylethyl-2-carboxylate)thio-5-thiolate-1,3,4-thiadiazole [0129]
  • Example 40 Example 40.
  • Example 41 Tetrasodium 2-(propyl-1,2,3-tricarboxylate)thio-5-thiolate- 1,3,4-thiadiazole [0130]
  • Example 41 Tetrapotassium 2-(propyl-1,2,3-tricarboxylate)thio-5-thiolate- 1,3,4-thiadiazole [0131]
  • Example 42 Synthesis of Diammonium 2-(propyl-2,3-dicarboxylate)thio-5- thiol-1,3,4-thiadiazole. 40g of the diacid product prepared in Example 29, 19g of aqueous ammonia solution, and 212.8 of deionized water were added to a 1-L flask and stirred under nitrogen at 25 oC for three hours.
  • Example 43 Synthesis of Triammonium 2-(propyl-1,2,3-tricarboxylate)thio- 5-thiol-1,3,4-thiadiazole. A procedure similar to Example 42 was used starting from the triacid prepared in Example 33 to prepare this product as a 20.3% weight solution in de- ionized water.
  • a DMTD derivative comprising, consisting essentially of, consisting of the reaction product of: a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of a: i. halo-ether group, ii. a halo-alcohol group, iii. an epoxide group, iv. a carboxamide group, v. a carboxylate group.
  • DMTD 2,5-dimercapto-1,3,4-thiadiazole
  • the DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a decyl group. [0148] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a undecyl group. [0149] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a dodecyl group.
  • the DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of an isobutyl group. [0151] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of an ethylhexyl group. [0152] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of an isoamyl group.
  • X comprises, consists essentially of, consists of, consists of, consists essentially of an alkali or alkaline earth metal, a trialkyl amine, a quaternary amine, or combinations thereof.
  • base com- prises consists essentially of, consists of, consists essentially of, or consists of Li.
  • base com- prises consists essentially of, consists of, consists essentially of, or consists of Na.
  • the substituent Y of the DMTD derivative of formula I is “[RO] o R,” where “o” is an integer from 1 to 100.
  • the ether (i.e., “[RO] o R,”) of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of dimethyl ether.
  • the DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of diethyl ether. [0168] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of dipropyl ether. [0169] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of methyl ethyl ether.
  • the DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of methyl phenyl ether. [0171] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of paraformaldehyde. [0172] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of polyethylene glycol.
  • R, m, n and o are as set forth for formula I.
  • substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of “R[OH] p A,” where “p” is an integer from 1 to 6 and “A” is H or an amine, such as a trialkyl amine or a quaternary amine salt.
  • the alcohol group i.e., the R[OH] p A group
  • the alcohol group comprises, consists essentially of, consists of propa- nol.
  • the DMTD derivative of paragraph 1 wherein the carboxylate is selected from ita- conate, citraconate, maleate, fumarate, mesaconate, where the carboxylates can be in the form of a salt with an alkali or alkaline earth metal, or an ester with an “R” group.
  • the carboxylate does not comprise a (meth)acrylate wherein the ester group of the (meth)acrylate comprises, consists essen- tially of, consists of H or an R group.
  • the reaction product com- prises consists essentially of, consists of a compound of formula where Z is X, RN + (R) 3 Cl-, RN + (R) 3 SO 3 -, RN + (R) 3 SO 3 -K + , RSO 3 -Na + , RSO 3 -NH 4 + , or RSO 3 H.
  • a zwitterionic DMTD derivative comprising, consisting essentially of, consisting of the reaction product of: a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of i. a linear, branched, saturated or unsaturated, cyclic halogenated C 1 to C 22 alkyl or aryl quaternary ammonium group, ii. a quaternary ammonium containing halo-ether group, iii. a quaternary ammonium containing halo-alcohol group, iv.
  • DMTD 2,5-dimercapto-1,3,4-thiadiazole
  • the zwitterionic DMTD derivative of any previous paragraph wherein the reaction product comprises, consists essentially of, consists of a compound of for- mula where R is as set forth in any previous paragraph.
  • the zwitterionic DMTD derivative of any previous paragraph wherein the reaction product comprises, consists essentially of, consists of a compound of for- mula where R and o are as set forth in any previous paragraph.
  • a bis-DMTD derivative comprising, consisting essentially of, consisting of the reaction product of a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of i.
  • reaction product comprises, consists essentially of, consists of a compound of formula where “m” is 1, 2 or 3, and “n” is 2; and where “Y” is: “R,” a linear, branched, saturated or unsaturated, or cyclic C1 to C12, or C1 to C 10 , or C 1 to C 8 , or even C 1 to C 6 alkyl or aryl group, or H; “CH 2 CH[CH 3 or H]C(O)OZ,” where “Z” is H, or a C 1 to C 22 alkyl or aryl group.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The disclosed technology relates to derivatives of 2,5-dimercapto-1,3,4-thiadiazole.

Description

TITLE 2,5-DIMERCAPTO-1,3,4-THIADIAZOLE (“DMTD”) DERIVATIVES BACKGROUND OF THE INVENTION [0001] The disclosed technology relates to derivatives of 2,5-dimercapto-1,3,4-thi- adiazole. [0002] Some simple alkyl and aryl substituted DMTD derivatives are known, for example, as taught in US 2,736,729, granted Feb. 28, 1956 to Krzikalla et al. and US3,212,892, granted Oct.19, 1965, to von König et al.. Simple acrylic acid alkyl and aryl esters of DMTD are also known, for example, as taught in JP 2013234126, pub- lished Nov.21, 2013 to Oya et al., and US 5,258,395, granted Nov.2, 1993 to Murase et al.. [0003] New chemistries are needed that can readily change oxidation states and are based on organic chemistry. Examples of such chemistry in the art usually start with some or all of relatively expensive starting materials and reagents, may need multiple steps to obtain the target final product, generate large quantities of undesir- able process wastes, and could also require tedious purification steps. SUMMARY OF THE INVENTION [0004] The disclosed technology, therefore, solves the problem of difficult to pro- duce and expensive but readily oxidizable organic chemistry by providing new DMTD derivatives that are synthesized in only one or two steps, starting from readily avail- able and inexpensive raw materials, use processing that generates little or no waste, and involve reactions which proceed rapidly and in high product conversions. [0005] One aspect of the technology is directed to a DMTD derivative obtained as the reaction product of: a) 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b) at least one of a: i) halo-ether group, ii) a halo-alcohol group, iii) an epoxide group, iv) a carboxamide group, and v) carboxylate group. [0006] In embodiments, any of the foregoing DMTD derivatives can be further reacted with a base. Similarly, any of the foregoing DMTD derivatives can be further reacted with an oxidizing reagent. [0007] The foregoing reaction products can include a mono-ether DMTD deriva- tive, in a salt form or not, or as a sulfur coupled bis-compound. [0008] The foregoing reaction products can include a mono-alcohol DMTD deriv- ative, in a salt form or not, or as a sulfur coupled bis-compound. [0009] The foregoing reaction products can include a mono-carboxamide DMTD derivative, in a salt form or not, or as a sulfur coupled bis-compound. [0010] The foregoing reaction products can include a mono-carboxylate DMTD de- rivative, in a salt form or not, or as a sulfur coupled bis-compound. [0011] Another aspect of the technology is directed to a DMTD derivative obtained as the reaction product of: a) 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b) at least one of a: i) a halogenated hydrocarbyl group, and ii) (meth)acrylate group, and c) an oxidizing agent. [0012] The foregoing reaction products can include a mono-alkyl bis-DMTD de- rivative. The foregoing reaction products can also include a mono-(meth)acrylate bis- DMTD derivative. [0013] Another aspect of the technology is directed to a zwitterionic DMTD derivative obtained as the reaction product of: a) 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b) at least one of: i) a linear, branched, saturated or unsaturated, cyclic halogenated C1 to C22 alkyl or aryl quaternary ammonium group, ii) a quaternary ammonium con- taining halo-ether group, iii) a quaternary ammonium containing halo-alcohol group, iv) a quaternary ammonium containing epoxide group, v) a quaternary ammonium containing carboxylate group, and vi) a quaternary ammonium containing carbox- amide group, and c) a strong base. [0014] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing alkyl DMTD derivative. [0015] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing ether DMTD derivative. [0016] The foregoing reaction products can also include a zwitterionic mono- qua- ternary ammonium containing alcohol DMTD derivative. [0017] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing (meth)acrylamide DMTD derivative. [0018] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing (meth)acrylate DMTD derivative. DETAILED DESCRIPTION OF THE INVENTION [0019] Various preferred features and embodiments will be described below by way of non-limiting illustration. [0020] Provided herein are derivatives of 2,5-Dimercapto-1,3,4-thiadiazole (“DMTD”). The DMTD derivatives include reaction products of DMTD and other chemical reagents via a variety of different chemical reactions. These reactions in- clude displacements using electron deficient hydrocarbons, 1,4-additions to olefins, and epoxide opening reactions, as well as acid-base reactions and disulfide formation (processes and co-reactants/catalysts for which are known in the art and readily en- visage by those of ordinary skill). These reactions can be performed in the presence of a wide array of functional groups that can provide for desired solubility and elec- trochemical performance. These functional groups include carbonyl-containing mol- ecules, heteroatom-containing molecules (nitrogen, oxygen, sulfur), inorganic atoms, and unsaturation. [0021] While the reaction products to prepare the derivatives often result in a mixture of products, the products can be provided as pure compounds as well. In general, the DMTD derivatives can be represented in the pure form by formula I: Formula I
Figure imgf000004_0001
where each “X” individually, is an alkali or alkaline earth metal, such as Li, Na, K, Mg, or Ca, a trialkyl amine, or a quaternary amine (including for purposes of this disclosure, ammonia), or H; “m” is 1, 2 or 3, and “n” is 1 or 2; and where “Y” is: “[RO]oR,” where “o” is an integer from 1 to 100; “R[OH]pA,” where “p” is an integer from 1 to 6 and “A” is H or an amine, such as a trialkyl amine or a quaternary amine salt; a carboxamide, such as a (meth)acrylamide of “CH2CH[CH3 or H]C(O)NHZ,” where “Z” is H, “R,” “RSO3-Na+,” “RSO3H,” or “RN+(R)3Cl-,” or a carboxylate, such as an itaconate, maleate, or, for example, a (meth)acrylate of “CH2CH[CH3 or H]C(O)OZ,” where “Z” can be X, RN+(R)3SO3-, RN+(R)3SO3-K+, “RSO3-Na+,” RSO3-NH4 +, “RSO3H,” or “RN+(R)3Cl-,” and where “R” is a linear, branched, saturated or unsaturated, or cyclic C1 to C12, or C1 to C10, or C1 to C8, or even C1 to C6 alkyl or aryl group, or H. [0022] Examples of the R group can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, including branched versions thereof, such as, for example, isobutyl, ethylhexyl, isoamyl, and the like, as well as aromatic groups (e.g. benzyl, phenyl, tolyl, xylyl, naphthyl, etc.) or cyclic groups (e.g., cyclohexyl). [0023] In preparing the DMTD derivatives, a base may be employed. Such a base may be, for example, an alkaline or alkaline earth metal hydroxide or carbonate, or an amine, such as, for example a trialkyl amine. If a base is employed, “X” in the foregoing formulas can be an alkali or alkaline earth metal such as Li, Na, K, Mg, or Ca, or a trialkyl amine. If a base is not employed, “X” would be H and the positive and negative charges associated therewith would be absent. [0024] In its un-coupled form, m and n in Formula I would both be 1, as shown in Formula II below. Formula II
Figure imgf000005_0001
[0025] The reaction products can also be further reacted with an oxidizing agent, such as, for example, hydrogen peroxide, to form a sulfur coupled “bis-” form of the particular derivative. In the case were the DMTD derivative is sulfur coupled, “n” in Formula I would be 2, “m” could be 1, 2 or 3, and “X” and the positive and negative charges associated therewith would be absent. Such coupled DMTD derivatives can be prepared by preparing the un-coupled compound and then introducing an oxidizing reagent, such as hydrogen peroxide or others, as would be known by those of ordinary skill in the art. Examples of coupled DMTD derivative are shown in Formulas III, IV and V below. Formula III
Figure imgf000006_0001
Formula IV
Figure imgf000006_0002
Formula V
Figure imgf000006_0003
[0026] In a particular embodiment, the DMTD derivatives can be the reaction product resulting from the displacement using electron deficient hydrocarbons be- tween DMTD and a halogenated ether (“halo-ether”) group (which include simple ethers as well as polyethers). The foregoing reaction product can further be reacted in an acid-base reaction with a base to form a salt or an oxidizing agent to form a bis- compound. [0027] As used herein, the term “group,” for example as in a halogenated alkyl or aryl group, halo-ether group, halo-alcohol group, (meth)acrylate group, and (meth)acrylamide group, depending on the context, refers to the structure of the stated group on its own or as the structure in which the group would form after reaction with another compound. For example, a methyl group could be CH4, as in its lone state, or -CH3 as in its bonded form, or, as a further example, methyl acrylate, could refer to CH2=CHC(O)OCH3, as in its lone state, or -CH2CH2C(O)OCH3, as in its bonded form. [0028] In the DMTD derivatives resulting from the displacement using electron deficient hydrocarbons between DMTD and a halo-ether group, the substituent Y of the DMTD derivatives of Formula I would be “[RO]oR,” with R and o as defined above. [0029] The mono-ether DMTD derivatives may be represented by formula VI: Formula VI
Figure imgf000007_0001
where X, R, m, and n are as set forth for Formula I, and “o” is an integer from 1 to 100, or 1 to 75, or 1 to 50, or 1 to 25, or 1 to 20, or 1 to 15, or 1 to 10, or 2 to 10 or 4 to 10 or 6 to 10. [0030] Where the mono-ether DMTD derivative is not reacted with a base, the mono-ether DMTD derivative would be represented by:
Figure imgf000007_0002
. [0031] Where the mono-ether DMTD derivative is reacted with a base, the mono-ether DMTD derivative would be represented by:
Figure imgf000008_0001
. [0032] Where the mono-ether DMTD derivative is reacted with an oxidizing reagent, the mono-ether DMTD derivative would be represented by:
Figure imgf000008_0002
. [0033] Example simple ethers (i.e., the [RO]oR group where o is 1) that may be employed include dimethyl ether (both R’s are methyl groups, o is 1), diethyl ether (both R’s are ethyl groups, o is 1), dipropyl ether (both R’s are propyl groups, o is 1), methyl ethyl ether (one R is a methyl group, one R is an ethyl group, o is 1), methyl phenyl ether (one R is a methyl group, one R is n phenyl group, o is 1). [0034] Example polyethers (i.e., the [RO]oR group where o is 2 to 100) that may be employed include paraformaldehyde (i.e., the [RO]oR group where the repeating R is a methyl group and the non-repeating R is H, o is 8 to 100), polyethylene glycol (i.e., the [RO]oR group where the repeating R is an ethyl group and the non-repeating R is H, o is 2 to 100), polypropylene glycol (i.e., the [RO]oR group where the repeat- ing R is an iso-propyl group and the non-repeating R is H, o is 2 to 100), polytetra- hydrofuran (i.e., the [RO]oR group where the repeating R is a butyl group and the non-repeating R is H, o is 2 to 100). [0035] In an example embodiment, DMTD can be reacted with a halomethyl ether, and optionally a base and/or oxidizing reagent, to provide a mono-ether DMTD de- rivative of one or more of formula VI(1), (2), (3), or (4).
Figure imgf000009_0001
[0036] In a further example embodiment, DMTD can be reacted with a polyeth- ylene glycol halide, and optionally a base and/or oxidizing reagent, to provide a mono-ether DMTD derivative of one or more of formula VI(5), (6), (7), or (8):
Figure imgf000010_0001
[0037] Similarly, the DMTD derivatives can be the reaction product resulting from the displacement using electron deficient hydrocarbons between DMTD and a halogenated alcohol (“halo-alcohol”) group. Similar DMTD derivatives can be pre- pared from an epoxide opening reaction between DMTD and an epoxide group. The foregoing reaction products can further be reacted in an acid-base reaction with a base to form a salt, or an oxidizing agent to form a bis- compound. [0038] In the alcohol containing DMTD derivatives resulting either from the dis- placement using electron deficient hydrocarbons between DMTD and a halo-alcohol, or from an epoxide opening reaction between DMTD and an epoxide group, the sub- stituent Y of the DMTD derivatives of Formula I would be “R[OH]pA,” and R, p and A as defined above. The mono-alcohol DMTD derivatives may be represented by formula VII: Formula VII
Figure imgf000011_0001
where X, R, m, and n are as set forth for Formula I, and “p” is an integer from 1 to 6 and “A” is H or an amine, such as a trialkyl amine or a quaternary amine salt. [0039] Where the mono-alcohol DMTD derivative is not reacted with a base, the mono-alco- hol DMTD derivative would be represented by:
Figure imgf000011_0002
. [0040] Where the mono-alcohol DMTD derivative is reacted with a base, the mono-alcohol DMTD derivative would be represented by:
Figure imgf000011_0003
. [0041] Where the mono-alcohol DMTD derivative is reacted with an oxidizing reagent, the mono-alcohol DMTD derivative would be represented by:
Figure imgf000012_0001
. [0042] Example mono-alcohols (i.e., the R[OH]pA group where p is 1 and A is H) include propanol (i.e., R is a linear or branched propyl group) which would be ob- tained, for example, from a halogenated propanol, such as chloropropanol or propyl- ene oxide; hexanol (i.e., R is a linear or branched hexyl group) which would be ob- tained, for example, from a halogenated hexanol, such as chlorohexanol; butanol (i.e., R is a linear or branched butyl group) which would be obtained, for example, from a halogenated butanol, such as chlorobutanol or butylene oxide; phenyl propanol (i.e., R is propyl or ethylbenzene) which would be obtained, for example, from a halogen- ated phenyl propanol group, such as chlorophenylethanol or styrene oxide. [0043] Example polyols (i.e., the R[OH]pA group where p is 2 to 6 and A is H) that may be employed include sugar alcohols, polyvinyl alcohols, ethylene glycol (i.e., R is an ethyl group, p is 2), propylene glycol (i.e., R is a linear or branched propyl group, p is 2), butanediol (i.e., R is a linear or branched butyl group, p is 2), glycerol (i.e., R is a butyl group, p is 3). [0044] Example alcohol amines (i.e., the R[OH]pA group where A is an amine) that may be employed include ethanolamine (i.e., R is an ethyl group, p is 1, A is NH2), propanolamine (i.e., R is a propyl group, p is 1, A is NH2), propanol dimethyl- amine (i.e., R is a propyl group, p is 1, A is N(CH3)2), propanol quaternary amine halide salt (i.e., R is a propyl group, p is 1, A is a N+(CH3)3•Cl-). [0045] In an example embodiment, DMTD can be reacted with a glycidol, and optionally a base and/or oxidizing reagent, to provide a mono-alcohol derivative of one or more of formula VII(1), (2), (3), or (4).
Figure imgf000013_0001
[0046] In a further example embodiment, DMTD can be reacted with a glycidol methacrylate, and optionally a base and/or oxidizing reagent, to provide a mono-al- cohol derivative of one or more of formula VII(5), (6), (7), or (8).
Figure imgf000014_0001
Figure imgf000015_0001
[0047] In a still further example embodiment, DMTD can be reacted with a 2- epoxy quaternary ethyl amine halide, and optionally a base and/or oxidizing reagent, to provide a mono-alcohol derivative of one or more of formula VII(9), (10), (11), or (12).
Figure imgf000015_0002
Figure imgf000016_0001
[0048] The DMTD derivatives can also be the reaction product resulting from a 1,4 addition between DMTD and a carboxamide group capable of 1,4 addition. The foregoing reaction product can further be reacted in an acid-base reaction with a base to form a salt or an oxidizing agent to form a bis- compound. [0049] Carboxamide groups capable of 1,4 addition can be readily envisaged by those of skill in the art, and include, both mono-carboxamides and di-carboxamides. Example carboxamides can include, but not be limited to, itaconic amide, citraconic amide, maleic amide, fumaric amide, mesaconic amide, as well as (meth)acrylamide. The carboxamides can be primary, or can be substituted with one or more “R” groups to form a secondary or tertiary amide group. [0050] As used herein, the parentheses “()” around the term “meth” means the term “meth” may or may not be present. Thus, (meth)acrylate can refer to both acrylate and methacrylate, and (meth)acrylamide includes both acrylamide and methacrylamide. [0051] In a particular example, carboxamide containing DMTD derivatives can result from 1,4 addition between DMTD and a (meth)acrylamide group, wherein the substituent Y of the DMTD derivatives of Formula I would be “CH2CH[CH3 or H]C(O)NHZ,” and Z is as defined above. Such mono-(meth)acrylamide DMTD de- rivatives may be represented by formula VIII: Formula VIII
Figure imgf000017_0001
where X, m, and n are as set forth for Formula I, and “Z” is H, “R,” RSO3-Na+, RSO3H, or RN+(R)3Cl-. [0052] Where the mono-(meth)acrylamide DMTD derivative is not reacted with a base, the mono-ether DMTD derivative would be represented by:
Figure imgf000017_0002
. [0053] Where the mono-(meth)acrylamide DMTD derivative is reacted with a base, the mono-ether DMTD derivative would be represented by:
Figure imgf000017_0003
. [0054] Where the mono-(meth)acrylamide DMTD derivative is reacted with an oxidizing reagent, the mono-ether DMTD derivative would be represented by:
Figure imgf000018_0001
. [0055] In some embodiments, DMTD can be reacted with methacrylaminopropyl trimethyl ammonium chloride to provide a mono-methacrylamide DMTD derivative of Formula VIII, in either coupled or un-coupled form, where Z (CH2)3N+(CH3)3Cl-, m is 1, 2 or 3 and n is 1 or 2 and X is an optional alkali or alkaline earth metal or amine. [0056] In some embodiments, DMTD can be reacted with 2-acrylamino-2- methylpropane sulfonic acid to provide a DMTD derivative of Formula VIII, in either coupled or un-coupled form, where Z is C(CH3)2CH2SO3H, m is 1, 2 or 3 and n is 1 or 2 and X is an optional alkali or alkaline earth metal or amine. [0057] In some embodiments, DMTD can be reacted with 2-acrylamino-2- methylpropane sulfonic acid sodium salt to provide a DMTD derivative of Formula VIII, in either coupled or un-coupled form, where Z is C(CH3)2CH2SO3-Na+, m is 1, 2 or 3 and n is 1 or 2 and X is an optional alkali or alkaline earth metal or amine. [0058] Likewise, the DMTD derivatives can also be the reaction product resulting from a 1,4 addition between DMTD and a carboxylate group capable of 1,4 addition. The foregoing reaction product can further be reacted in an acid-base reaction with a base to form a salt or an oxidizing agent to form a bis- compound. [0059] Carboxylate groups capable of 1,4 addition can be readily envisaged by those of skill in the art, and include, both mono-carboxylates and di-carboxylates as well as higher carboxylates, e.g., tricarboxylates, tetracarboxylates, etc. Example car- boxylates can include, but not be limited to, itaconates, citraconates, maleates, fumarates, mesaconates, as well as (meth)acrylates. The carboxylates can be in the form of a salt with an alkali or alkaline earth metal, an ammonia group, or an ester with an “R” group. Where the salt is desired, it can be obtained by 1,4 addition of the salted monomer, or by addition of the ester followed by saponification with an alkali or alkaline earth metal hydroxide or ammonium hydroxide. In some embodiments, the carboxylate does not include a (meth)acrylic acid or a (meth)acrylate where the ester group of the (meth)acrylate is a simple R group. [0060] In general, the carboxylate containing DMTD derivatives can result from 1,4 addition between DMTD and a carboxylic acid or carboxylate. Where the 1,4 ad- dition is with a carboxylic acid, the reaction will be followed by reaction with the de- sired base to form the salt. For example, DMTD may be reacted with aconitic acid to form a DMTD derivative with an aconitic acid connected off of a substituent sulfur, followed by reaction with an alkali metal hydroxide, alkali earth metal hydroxide, or ammonium hydroxide. Such a reaction could be represented, for example, by the fol- lowing reaction mechanism:
Figure imgf000019_0001
[0061] A further example could be a carboxylate containing DMTD derivative re- sulting from the 1,4 addition between DMTD and a dialkyl itaconate, such as dime- thyl itaconate, wherein the substituent Y of the DMTD derivatives of Formula I would be dimethyl itaconate, for example, as represented by formula
Figure imgf000020_0001
. [0062] In the foregoing example, the carboxylate could also be, for example, a di- alkali or dialkaline earth itaconate salt, such disodium itaconate, represented, for ex- ample, by formula
Figure imgf000020_0002
. [0063] Another example carboxylate containing DMTD derivative can result from 1,4 addition between DMTD and a dialkyl maleate, such as dimethyl maleate, wherein the substituent Y of the DMTD derivatives of Formula I would be dimethyl maleate, for example, as represented by formula
Figure imgf000021_0001
. [0064] In the foregoing example, the carboxylate could also be, for example, a di- alkali or dialkaline earth maleate salt, such disodium maleate, represented, for exam- ple, by formula
Figure imgf000021_0002
. [0065] Further examples can include, for example, the reaction of methyl acrylate and DMTD, or dimethyl maleate and DMTD. Where the salts are desired, these exam- ples can also include, for example, the reaction of sodium acrylate or disodium maleate, or the foregoing esters could be saponified in the presence of sodium hydroxide to obtain the salts. [0066] In further examples, a carboxylate containing DMTD derivatives can result from 1,4 addition between DMTD and a (meth)acrylate group in which the ester group is a quaternary ammonium group or a sulfur trioxide containing group, wherein the substituent Y of the DMTD derivatives of Formula I would be “CH2CH[CH3 or H]C(O)OZ.” The mono-(meth)acrylate DMTD derivatives may be represented by formula IX: Formula IX
Figure imgf000022_0001
where X, m, and n are as set forth for Formula I, and “Z” is X, RSO3-Na+, RSO3H, RN+(R)3SO3-, RN+(R)3SO3-K+, RSO3-NH4 + or RN+(R)3Cl-. [0067] Where the mono-(meth)acrylate DMTD derivative is not reacted with a base, the mono-ether DMTD derivative would be represented by:
Figure imgf000022_0002
where Z is X, RSO3-Na+, RSO3H, RN+(R)3SO3-, RN+(R)3SO3-K+, RSO3-NH4 + or RN+(R)3Cl-. [0068] Where the mono-(meth)acrylate DMTD derivative is reacted with a base, the mono-ether DMTD derivative would be represented by:
Figure imgf000022_0003
where Z is X, RSO3-Na+, RSO3H, RN+(R)3SO3-, RN+(R)3SO3-K+, RSO3-NH4 + or RN+(R)3Cl-. [0069] Where the mono-(meth)acrylate DMTD derivative is reacted with an oxidizing re- agent, the mono-ether DMTD derivative would be represented by:
Figure imgf000023_0001
where Z is X, RSO3-Na+, RSO3H, RN+(R)3SO3-, RN+(R)3SO3-K+, RSO3-NH4 + or RN+(R)3Cl-. [0070] In an example embodiment, DMTD can be reacted with methacryloxyethyl trimethyl ammonium chloride to provide a mono-methacrylate DMTD derivative of Formula IX, in either coupled or un-coupled form, where Z is (CH2)2N+(CH3)3Cl-, m is 1, 2 or 3 and n is 1 or 2 and X is an optional alkali or alkaline earth metal or amine. [0071] Likewise, the DMTD derivatives can also be the reaction product resulting from a 1,4 addition between DMTD and a (meth)acrylate group and an oxidizing agent to form a bis- compound. [0072] In bis-(meth)acrylate containing DMTD derivatives resulting from 1,4 ad- dition between DMTD and a (meth)acrylate group and an oxidizing agent, the sub- stituent Y of the DMTD derivatives of Formula I would be “CH2CH[CH3 or H]C(O)OZ,” and Z is R or H. The mono-(meth)acrylate DMTD derivatives may be represented by formula X: Formula X
Figure imgf000023_0002
where m is 1, 2 or 3 and “Z” is R or H. [0073] In an example embodiment, DMTD can be reacted with methyl acrylate, followed by an oxidizing agent to provide mono-acrylate bis-DMTD derivative of Formula X, where Z is CH3, and m is 1, 2 or 3. [0074] In another example embodiment, DMTD can be reacted with 2-ethylhexyl acrylate, followed by an oxidizing agent, to provide a mono-acrylate bis-DMTD de- rivative of Formula X where Z is a 2-ethylhexyl group, and m is 1, 2 or 3. [0075] The DMTD derivatives can also be the reaction product resulting from the displacement using electron deficient hydrocarbons between DMTD and a halogen- ated hydrocarbyl (“halo-hydrocarbyl”) group (which include linear, branched, satu- rated or unsaturated, or cyclic alkyl group, or aryl group, where an unsaturated alkyl group is synonymous with an alkene), and further reacted with an oxidizing agent to form a bis- compound. [0076] In the DMTD derivatives resulting from the displacement using electron deficient hydrocarbons between DMTD and a halo-hydrocarbyl group, the substituent Y of the DMTD derivatives of Formula I would be “R,” as defined above, n would be 2 and m would be 1, 2 or 3. Although the substituent may be any hydrocarbyl group, the derivative is collectively referred to herein and in the claims as a “mono- alkylated” DMTD derivative. [0077] The mono-alkylated bis-DMTD derivatives may be represented by formu- las XI: Formula XI
Figure imgf000024_0001
where m is 1, 2 or 3, and R is a linear, branched, saturated or unsaturated, cyclic C1 to C12, or C1 to C10, or C1 to C8, or even C1 to C6 alkyl or aryl group; or H. [0078] In an example embodiment, DMTD can be reacted with a benzylhalide and an oxidizing reagent, to provide a mono-arylated DMTD derivative of one or more of formula XI(1), (2), or (3).
Figure imgf000025_0001
[0079] In some embodiments, DMTD derivatives such as those discussed above may include a quaternary ammonium substituent and be treated with a strong base, such as LiOH, NaOH, KOH, Ca(OH)2, a quaternary amine such as R4NOH, and the like to produce a zwitterionic species. [0080] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing alkyl DMTD derivative represented as shown in formula XII:
Figure imgf000026_0001
[0081] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing ether DMTD derivative represented as shown in formula XIII:
Figure imgf000026_0002
[0082] The foregoing reaction products can also include a zwitterionic mono- qua- ternary ammonium containing alcohol DMTD derivative represented as shown in for- mula XIV:
Figure imgf000026_0003
[0083] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing carboxamide, such as, for example, a (meth)acrylamide DMTD derivative represented as shown in formula XV: Formula XV
Figure imgf000026_0004
[0084] The foregoing reaction products can include a zwitterionic mono- quater- nary ammonium containing carboxylate, such as, for example, a (meth)acrylate DMTD derivative represented as shown in formula XVI:
Figure imgf000027_0001
[0085] For example, DMTD can be reacted with methacrylaminopropyl trimethyl ammonium chloride to provide a mono-methacrylamide DMTD derivative of For- mula XV where Z (CH2)3N+(CH3)3Cl-, m is 1, 2 or 3 and n is 1 or 2, followed by treatment with NaOH to afford a zwitterion of formula XV’: Formula XV’
Figure imgf000027_0002
. [0086] The amount of each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial ma- terial, that is, on an active chemical basis, unless otherwise indicated. However, unless otherwise indicated, each chemical or composition referred to herein should be inter- preted as being a commercial grade material which may contain the isomers, by-prod- ucts, derivatives, and other such materials which are normally understood to be present in the commercial grade. EXAMPLES [0087] Example 1. Synthesis of 2-(2-Hydroxyethylcarboxyethyl)thio-5-thiol- 1,3,4-Thiadiazole. 150.2 grams of DMTD, 150 grams of toluene solvent, and 120 grams of 97% pure 2-hydroxyethyl acrylate were added to a 1-liter flask and heated at 85 ºC for five hours. Toluene solvent was vacuum stripped on a rotary evaporator at 3 mm Hg vacuum and 80 ºC for four hours. The product was obtained as a viscous yellow liquid after filtration through silicon dioxide filter aid. [0088] Example 2. Synthesis of 2-(2-Ethoxyethoxycarboxyethyl)thio-5-thiol- 1,3,4-Thiadiazole 150.2 grams of DMTD, 150 grams of toluene solvent, and 188.2 grams of 2-ethoxyethoxy acrylate were added to a 1-liter flask and heated at 85 ºC for two hours. Toluene solvent was vacuum stripped on a rotary evaporator at 3 mm Hg vacuum and 80 ºC for four hours. The product was obtained as a viscous yellow liquid. [0089] Example 3. Synthesis of 2-(Methacryloylaminopropyltrimethylammo- nium chloride)thio-5-thiol-1,3,4-Thiadiazole. 84.1 grams of DMTD, 247 grams of 50% aqueous Methacryloylaminopropyltrimethylammonium chloride, 0.42 gram of sodium hydroxide, and 300 grams of water were added to a one liter flask and heated under nitrogen at 90 ºC for 8 hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 2 mm Hg and 95 ºC for 20 hours. The final product was a crystalline solid. [0090] Example 4. Synthesis of 2-(Methacryloylaminopropyltrimethylammo- nium)thio-5-thiolate-1,3,4-Thiadiazole. 122.7 grams of 2-(Methacry- loylaminopropyltrimethylammonium chloride) thio-5-thiol-1,3,4-Thiadiazole, 13.2 grams of sodium hydroxide, and 200 grams of deionized water were added to a one liter flask and heated under nitrogen at 70 ºC for three hours. The mixture was trans- ferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 5 mm Hg and 95 ºC for 18 hours. The crystalline solid obtained was dissolved in 250 mL of ethanol and cooled to pre- cipitate sodium chloride, which was removed by filtration. Ethanol was removed in a 65 ºC oven and a vacuum oven to constant weight at 95 ºC. [0091] Example 5. Synthesis of 2-(Acryloylamino-2-methylpropylsulfonic acid)thio-5-thiol-1,3,4-thiadiazole. 98.15 grams of DMTD, 135.4 grams of 2- Acrylamido-2-methylpropanesulfonic acid, 0.2 gram of sodium hydroxide, and 200 grams of isopropanol solvent were added to a one liter flask and heated under nitrogen at 80 ºC for 8 hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 4 mm Hg and 95 ºC for 22 hours. The final product was a crystalline solid. [0092] Example 6. Synthesis of Sodium 2-(Acryloylamino-2-methylpropyl- sulfonate)thio-5-thiol-1,3,4-thiadiazole. 150.2 grams of DMTD, 320.9 grams of 50% aqueous 2-Acrylamido-2-methylpropanesulfonic acid sodium salt, 80 grams of de- ionized water solvent were added to a one liter flask and heated under nitrogen at 80 ºC for 6 hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 3 mm Hg and 100 ºC for 16 hours. The final product was a crystalline solid. [0093] Example 7. Synthesis of Disodium 2-(Acryloylamino-2-methylpropyl- sulfonate)thio-5-thiolate-1,3,4-thiadiazole. 72.7 grams of 2-(Acryloylamino-2- methylpropylsulfonic acid)-5-thiol-1,3,4-thiadiazole prepared in Example 16, 16.25 grams of sodium hydroxide, 200 grams of deionized water solvent were added to a one liter flask and heated under nitrogen at 85 ºC for 3 hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 3 mm Hg and 105 ºC for 16 hours. The final product was a crystalline solid. [0094] Example 8. Synthesis of 2-(Methacryloyloxyethyl trimethylammonium chloride)thio-5-thiol-1,3,4-Thiadiazole. 65.9 grams of DMTD, 126.5 grams of 72% aqueous Methacryloyloxyethyltrimethylammonium chloride, 0.2 gram of sodium hy- droxide, and 125 grams of water were added to a one liter flask and heated under nitrogen at 90 ºC for 8 hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 2.5 mm Hg and 95 ºC for 23 hours. The final product was a crys- talline solid. [0095] Example 9. Synthesis of 2-(2-hydroxypropyltrimethylammonium chlo- ride)thio-5-thiol-1,3,4-thiadiazole. 45.07 grams of DMTD, 45.9 grams of technical grade glycidyltrimethylammonium chloride, and 200 grams of reagent grade acetoni- trile solvent were added to a one liter flask and heated under nitrogen at 80 ºC for 8 hours. The mixture was transferred to an open beaker and most of the solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 3.5 mm Hg and 90 ºC for 22 hours. The final product was a yellow crystalline solid. [0096] Example 10. Synthesis of bis-2-(n-Hexyl-5-disulfide)-1,3,4-thiadiazole. 229 grams of 2-(n-Hexyl)thio-5-thiol-1,3,4-Thiadiazole prepared in Example 24 was added to a one liter flask and 55.4 grams of 35% hydrogen peroxide in water was added over 45 minutes while keeping the temperature in the range of 75-80 ºC under nitrogen. The reaction was heated at 85 ºC for four hours, cooled, and dissolved into 300 mL of reagent grade toluene. This solution was washed with additional deionized water using a separatory funnel, collected, and dried over anhydrous sodium sulfate. The toluene solvent was removed using a rotary evaporator to obtain the disulfide as a low melting wax. [0097] Example 11. Synthesis of Sodium 2-(n-Hexyl)thio-5-thiolate-1,3,4-Thi- adiazole. 42.5 grams of 2-(n-Hexyl)thio-5-thiol-1,3,4-Thiadiazole prepared in Ex- ample 24, 7.25 grams of sodium hydroxide, and 200 mL of toluene solvent were added to a 1-L flask and heated at reflux for 6 hours. Water distillate was collected using a Dean Stark trap. The reaction mixture was transferred to an open beaker and most of the solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 2 mm Hg and 90 ºC for 18 hours. The final product was a light yellow solid. [0098] Example 12. Synthesis of 2-[(Methacryloyloxy)ethyl-dimethyl-(3- sulfopropyl)ammonium]thio-5-thiol-1,3,4-Thiadiazole. 86.6 grams of [2-(Methacry- loyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 46.6 grams of DMTD, 0.3 gram of sodium hydroxide, and 250 grams of deionized water were added to a one liter flask and heated under nitrogen at 85 ºC for six hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 3 mm Hg and 85 ºC for 18 hours. The product was obtained as a glasslike solid. [0099] Example 13. Synthesis of Potassium 2-[(Methacryloyloxy)ethyl-di- methyl-(3-sulfopropyl)ammonium]thio-5-thiolate-1,3,4-Thiadiazole. 59.3 grams of [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 40 grams of DMTD mono-potassium salt, 0.3 gram of potassium hydroxide, and 200 grams of deionized water were added to a one liter flask and heated under nitrogen at 85 ºC for six hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 5 mm Hg and 85 ºC for 20 hours. The product was obtained as a yellow solid. [0100] Example 14. Synthesis of Potassium 2-[(Methacryloyloxy-3-sulfopro- pyl)thio-5-thiol-1,3,4-Thiadiazole. 73.9 grams of 3-sulfopropyl methacrylate potas- sium salt, 45.07 grams of DMTD, 0.2 gram of sodium hydroxide, and 250 grams of deionized water were added to a one liter flask and heated under nitrogen at 85-90 ºC for 12 hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 3 mm Hg and 90 ºC for 28 hours. The product was obtained as a yellow solid. [0101] Example 15. Synthesis of Dipotassium 2-[(Methacryloyloxy-3-sul- fopropyl)thio-5-thiolate-1,3,4-Thiadiazole. 49.7 grams of 3-sulfopropyl methacry- late potassium salt, 38 grams of DMTD mono-potassium salt, 0.3 gram of potassium hydroxide, and 225 grams of deionized water were added to a one liter flask and heated under nitrogen at 85 ºC for six hours. The clear mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on stand- ing, followed by vacuum drying at 3.5 mm Hg and 95 ºC for 24 hours. The product was obtained as an amber solid. [0102] Example 16. Synthesis of Dipotassium 2-(2-methylethyl-2-carbox- ylate)thio-5-thiolate-1,3,4-Thiadiazole. 100 grams of ester prepared in Example 23, 44.8 grams of potassium hydroxide, and 300 grams of deionized water were added to a one liter flask and heated at reflux (90 ºC) for 14 hours while collecting distillate in a Dean Stark trap. The clear mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 4.5 mm Hg and 95 ºC for 26 hours. The product was obtained as a light yellow crystalline solid. [0103] Example 17. Synthesis of Disodium 2-(Propyl-2,3-dicarbox- ylate)thio-5-thiol-1,3,4-Thiadiazole. 65.25 grams of Itaconic acid, 75.1 grams of DMTD, 0.3 gram of sodium hydroxide, and 200 grams of deionized water were added to a one liter flask and heated under nitrogen at 90 ºC for six hours. The clear mixture was cooled to room temperature and 40 grams of sodium hydroxide addded, followed by heating at 70 ºC for four hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 4 mm Hg and 95 ºC for 26 hours. The product was obtained as a yellow solid powder. [0104] Example 18. Synthesis of Trisodium 2-(Propyl-2,3-dicarbox- ylate)thio-5-thiolate-1,3,4-Thiadiazole. 40 grams of DMTD mono-sodium salt, 30.2 grams of Itaconic acid, and 250 grams of deionized water were added to a one liter flask. 18.6 grams of sodium hydroxide was then added the mixture heated under nitrogen at 90 ºC for 12 hours. The mixture was cooled to room temperature and a small amount of insoluble solid removed through filter paper. The clear mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 2 mm Hg and 100 ºC for 28 hours. The product was obtained as a yellow solid powder. [0105] Example 19. Synthesis of Disodium 2-(Ethyl-2,3-dicarboxylate)thio- 5-thiol-1,3,4-Thiadiazole. 46.45 grams of maleic acid, 60.1 grams of DMTD, 0.25 gram of sodium hydroxide, and 175 grams of deionized water were added to a one liter flask and heated under nitrogen at 90 ºC for six hours. The clear mixture was cooled to room temperature and 32 grams of sodium hydroxide addded, followed by heating at 70 ºC for four hours. The mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 2 mm Hg and 95 ºC for 24 hours. The product was obtained as a yellow solid. [0106] Example 20. Synthesis of Disodium 2-(2-methylethyl-2-carbox- ylate)thio-5-thiolate-1,3,4-Thiadiazole. 35 grams of DMTD mono-sodium salt, 22 grams of sodium methacrylate, 0.3 gram of sodium hydroxide catalyst, and 200 grams of deionized water solvent were added to a one liter flask and heated at 90 ºC for 8 hours and cooled. A small amount of an insoluble solid was removed by filtration through filter paper. The clear mixture was transferred to an open beaker and most of the water solvent was evaporated in a 65 ºC oven on standing, followed by vacuum drying at 2.5 mm Hg and 95 ºC for 24 hours. The product was obtained as a light yellow solid. [0107] Example 21. Synthesis of 2-(2-Ethylhexylcarboxyethyl)thio-5-thiol-1,3,4- Thiadiazole. 150.2 grams of DMTD, 150 grams of toluene solvent, and 184.3 grams of 2- ethylhexyl acrylate were added to a 1-liter flask and heated at 85 ºC for 7 hours. Toluene solvent was vacuum stripped on a rotary evaporator at 2 mm Hg vacuum and 80 ºC for 5 hours to provide the desired product as a yellow liquid. [0108] Example 22. Synthesis of 2-(Laurylcarboxy-2-methylethyl)thio-5-thiol- 1,3,4-Thiadiazole. 129 grams of DMTD, 216.2 grams of lauryl methacrylate, and 0.2 gram of sodium hydroxide catalyst were added to a one liter flask and heated at 105 ºC for 14 hours after which time the reaction was clear and all of the starting materials had dissolved. The mixture was vacuum stripped on a rotary evaporator for six hours at 2 mm Hg vacuum and 80 ºC to provide the desired product as a low melting solid. [0109] Example 23. Synthesis of 2-(Methylcarboxy-2-methylethyl)thio-5-thiol- 1,3,4-Thiadiazole. 182.1 grams of DMTD, 121.3 grams of methyl methacrylate, 0.3 gram of potassium t-butoxide catalyst, and 400 mL of toluene solvent were added to a two liter flask and heated at 100 ºC for 12 hours after which time a small amount of a yellow solid was removed by filtration. The mixture was vacuum stripped on a rotary evaporator for six hours at 2 mm Hg vacuum and 80 ºC to provide the desired product as a yellow solid upon cooling. [0110] Example 24. Synthesis of 2-(n-Hexyl)thio-5-thiol-1,3,4-Thiadiazole. 150.2 grams of DMTD and 900 mL of ethanol were added to a 3-L flask and 56.1 grams of potassium hydroxide was added in portions over a 30 minute period. The reaction was heated at 75 ºC for 2 hours under nitrogen and cooled to 24 ºC. 165.1 grams of n-hex- ylbromide was added over 20 minutes and the mixture heated at reflux (77 ºC) for 6 hours. Ethanol was distilled from the reaction and the residue dissolved into 400 grams of wa- ter/600 mL of toluene and transferred to a separatory funnel. The organic phase was washed with additional water, collected, and dried over anhydrous sodium sulfate. After removal of the toluene on a rotary evaporator, the low-melting solid obtained was recrys- tallized from reagent grade toluene:n-hexane (80:20) wt.:wt. and dried in a vacuum oven to obtain the pure product. [0111] Examples 25- 28. Using a similar procedure as Example 24 from the corre- sponding alkyl bromides, the following DMTD mono-alkylates were prepared: [0112] Example 25. 2-(2-Ethylhexyl)thio-5-thiol-1,3,4-Thiadiazole [0113] Example 26. 2-Cyclohexylthio-5-thiol-1,3,4-Thiadiazole [0114] Example 27. 2-Isoamylthio-5-thiol-1,3,4-Thiadiazole [0115] Example 28. 2-(Ethylcarboxymethylene)thio-5-thiol-1,3,4-Thiadiazole [0116] Example 29. Synthesis of 2-(2,3-Dicarboxypropyl)thio-5-thiol-1,3,4-Thiadi- azole. 105.16g of 2,5-dimercapto-1,3,4-thiadiazole, 300g of deionized water, 91.1g of it- aconic acid and 0.3g of sodium hydroxide catalyst were added to a 1-L flask and heated under nitrogen at 88 ºC for 10 hours and cooled. Most of the water was evaporated in a steam oven at 65 ºC in an open beaker. The product was then dried in a vac oven at 95 ºC until constant weight. The product yield was 194g. [0117] Examples 30-33. A procedure similar to Example 29 was used starting from acrylic acid, methacrylic acid, maleic acid, or aconitic acid to prepare the fol- lowing: [0118] Example 30. 2-(2-Carboxyethyl)thio-5-thiol-1,3,4-thiadiazole [0119] Example 31. 2-(2-Methylethyl-2-carboxy)thio-5-thiol-1,3,4-thiadiazole [0120] Example 32. 2-(2,3-Dicarboxyethyl)thio-5-thiol-1,3,4-thiadiazole [0121] Example 33. 2-(1,2,3-Tricarboxypropyl)thio-5-thiol-1,3,4-thiadiazole [0122] Example 34 (Alternate procedure for Example 18) Synthesis of Trisodium 2- (propyl-2,3-dicarboxylate)thio-5-thiolate-1,3,4-thiadiazole. 32g of the diacid product pre- pared in Example 29, 250g of deionized water, and 13.7g of sodium hydroxide were added to a 1-L flask and heated under nitrogen at 85 ºC for 6 hours. The mixture was transferred to an open beaker and most of the water evaporated in a steam oven at 65 ºC. The product was dried in a vacuum oven at 95 ºC to constant weight to obtain 38.8g of a light yellow solid. [0123] Examples 35-41. The procedure of Example 34 was used to prepare the fol- lowing products from the corresponding carboxylic acids of Examples 29-33: [0124] Example 35. Dipotassium 2-(ethyl-2-carboxylate)thio-5-thiolate-1,3,4-thiadi- azole [0125] Example 36. Tripotassium 2-(ethyl-1,2-dicarboxylate)thio-5-thiolate-1,3,4- thiadiazole [0126] Example 37. Tripotassium 2-(propyl-2,3-dicarboxylate)thio-5-thiolate-1,3,4- thiadiazole [0127] Example 38. (Alternate procedure for Example 16) Dipotassium 2-(2-meth- ylethyl-2-carboxylate)thio-5-thiolate-1,3,4-thiadiazole [0128] Example 39. (Alternate procedure for Example 20). Disodium 2-(2-meth- ylethyl-2-carboxylate)thio-5-thiolate-1,3,4-thiadiazole [0129] Example 40. Tetrasodium 2-(propyl-1,2,3-tricarboxylate)thio-5-thiolate- 1,3,4-thiadiazole [0130] Example 41. Tetrapotassium 2-(propyl-1,2,3-tricarboxylate)thio-5-thiolate- 1,3,4-thiadiazole [0131] Example 42. Synthesis of Diammonium 2-(propyl-2,3-dicarboxylate)thio-5- thiol-1,3,4-thiadiazole. 40g of the diacid product prepared in Example 29, 19g of aqueous ammonia solution, and 212.8 of deionized water were added to a 1-L flask and stirred under nitrogen at 25 ºC for three hours. The reaction mixture was clear and free of solids. 271g of a 20% weight product solution in water was obtained. [0132] Example 43. Synthesis of Triammonium 2-(propyl-1,2,3-tricarboxylate)thio- 5-thiol-1,3,4-thiadiazole. A procedure similar to Example 42 was used starting from the triacid prepared in Example 33 to prepare this product as a 20.3% weight solution in de- ionized water. [0133] Each of the documents referred to above is incorporated herein by reference, including any prior applications, whether or not specifically listed above, from which priority is claimed. The mention of any document is not an admission that such docu- ment qualifies as prior art or constitutes the general knowledge of the skilled person in any jurisdiction. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction con- ditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word "about." It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used to- gether with ranges or amounts for any of the other elements. [0134] As used herein, the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of “comprising” herein, it is intended that the term also encompass, as alter- native embodiments, the phrases “consisting essentially of” and “consisting of,” where “consisting of” excludes any element or step not specified and “consisting essentially of” permits the inclusion of additional un-recited elements or steps that do not materi- ally affect the essential or basic and novel characteristics of the composition or method under consideration. [0135] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without de- parting from the scope of the subject invention. In this regard, the scope of the in- vention is to be limited only by the following claims. [0136] A DMTD derivative comprising, consisting essentially of, consisting of the reaction product of: a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of a: i. halo-ether group, ii. a halo-alcohol group, iii. an epoxide group, iv. a carboxamide group, v. a carboxylate group. [0137] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula I Formula I
Figure imgf000037_0001
where each “X,” individually, is an alkali or alkaline earth metal, such as Li, Na, K, Mg, or Ca, a trialkyl amine, or a quaternary amine (including ammonia), or H; “m” is 1, 2 or 3, and “n” is 1 or 2; and where “Y” is: “[RO]oR,” where “o” is an integer from 1 to 100; “R[OH]pA,” where “p” is an integer from 1 to 6 and “A” is H or an amine, such as a trialkyl amine or a quaternary amine salt; a carboxamide, such as a (meth)acrylamide of “CH2CH[CH3 or H]C(O)NHZ,” where “Z” is H, “R,” “RSO3-Na+,” “RSO3H,” or “RN+(R)3Cl-,” or a carboxylate, such as an itaconate, maleate, or, for example, a (meth)acrylate of “CH2CH[CH3 or H]C(O)OZ,” where “Z” can be X, RN+(R)3SO3-, RN+(R)3SO3-K+, “RSO3-Na+,” RSO3-NH4 +, “RSO3H,” or “RN+(R)3Cl-,” and where “R” is a linear, branched, saturated or unsaturated, or cyclic C1 to C12, or C1 to C10, or C1 to C8, or even C1 to C6 alkyl or aryl group, or H. [0138] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a methyl group. [0139] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of an ethyl group. [0140] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a propyl group. [0141] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a butyl group. [0142] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a pentyl group. [0143] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a hexyl group. [0144] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a heptyl group. [0145] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of an octyl group. [0146] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a nonyl group. [0147] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a decyl group. [0148] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a undecyl group. [0149] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a dodecyl group. [0150] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of an isobutyl group. [0151] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of an ethylhexyl group. [0152] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of an isoamyl group. [0153] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a benzyl group. [0154] The DMTD derivative of any previous paragraph, wherein the “R” group comprises, consists essentially of, consists of, consists essentially of, consists of a cyclohexyl group. [0155] The DMTD derivative of any previous paragraph, wherein “X” comprises, consists essentially of, consists of, consists of, consists essentially of H. [0156] The DMTD derivative of any previous paragraph, wherein the reaction product further comprises, consists essentially of, consists of reaction with a base. [0157] The DMTD derivative of any previous paragraph, wherein “X” comprises, consists essentially of, consists of, consists of, consists essentially of an alkali or alkaline earth metal, a trialkyl amine, a quaternary amine, or combinations thereof. [0158] The DMTD derivative of any previous paragraph, wherein the base com- prises, consists essentially of, consists of, consists essentially of, or consists of Li. [0159] The DMTD derivative of any previous paragraph, wherein the base com- prises, consists essentially of, consists of, consists essentially of, or consists of Na. [0160] The DMTD derivative of any previous paragraph, wherein the base com- prises, consists essentially of, consists of, consists essentially of, or consists of K. [0161] The DMTD derivative of any previous paragraph, wherein the base com- prises, consists essentially of, consists of, consists essentially of, or consists of Mg. [0162] The DMTD derivative of any previous paragraph, wherein the base com- prises, consists essentially of, consists of, consists essentially of, or consists of Ca. [0163] The DMTD derivative of any previous paragraph, wherein the reaction product further comprises, consists essentially of, consists of reaction with an oxidizing reagent. [0164] The DMTD derivative of any previous paragraph, wherein the reaction product further comprises, consists essentially of, consists of reaction with hydrogen peroxide. [0165] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I is “[RO]oR,” where “o” is an integer from 1 to 100. [0166] The DMTD derivative of any previous paragraph, wherein the ether (i.e., “[RO]oR,”) of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of dimethyl ether. [0167] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of diethyl ether. [0168] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of dipropyl ether. [0169] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of methyl ethyl ether. [0170] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of methyl phenyl ether. [0171] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of paraformaldehyde. [0172] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of polyethylene glycol. [0173] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of polypropylene glycol. [0174] The DMTD derivative of any previous paragraph, wherein the ether of the halogenated ether comprises, consists essentially of, consists of, consists essentially of, consists of polytetrahydrofuran. [0175] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000041_0001
where R, X, o, m and n are as set forth for formula I. [0176] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000041_0002
where R and o are as set forth for formula I. [0177] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000041_0003
where R, X and o are as set forth for formula I. [0178] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000042_0001
where R, m, n and o are as set forth for formula I. [0179] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of “R[OH]pA,” where “p” is an integer from 1 to 6 and “A” is H or an amine, such as a trialkyl amine or a quaternary amine salt. [0180] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of propa- nol. [0181] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of hexa- nol. [0182] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of buta- nol. [0183] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of phenyl propanol. [0184] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of a sugar alcohol. [0185] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of a pol- yvinyl alcohol. [0186] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of eth- ylene glycol. [0187] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of pro- pylene glycol. [0188] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of bu- tanediol. [0189] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of glyc- erol. [0190] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of etha- nolamine. [0191] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of pro- panolamine. [0192] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of propa- nol dimethylamine. [0193] The DMTD derivative of any previous paragraph, wherein the alcohol group (i.e., the R[OH]pA group) comprises, consists essentially of, consists of a pro- panol quaternary amine halide salt. [0194] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000044_0001
where X, m, n, p, and A are as set forth for formula I. [0195] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000044_0002
where p and A are as set forth for formula I. [0196] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000044_0003
where X, p and A are as set forth for formula I. [0197] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000044_0004
where m, n, p, and A are as set forth for formula I. [0198] The DMTD derivative of any previous paragraph, wherein the DMTD de- rivative comprises, consists essentially of, consists of the reaction product of DMTD and a carboxamide group. [0199] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a carboxamide group. [0200] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a mono-carboxamide group. [0201] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a di-carboxamide group. [0202] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a primary carboxamide group. [0203] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a secondary carboxamide group. [0204] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a tertiary carboxamide group. [0205] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of an itaconic amide group. [0206] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a maleic amide group. [0207] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a citraconic amide group. [0208] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a fumaric amide group. [0209] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a mesaconic amide group. [0210] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of a (meth)acrylamide group. [0211] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of “CH2CH[CH3 or H]C(O)NHZ,” where “Z” can be H, “R,” “RSO3-Na+,” “RSO3H,” or “RN+(R)3Cl-.” [0212] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula IX
Figure imgf000046_0001
where X, m, n and Z are as set forth for formula I. [0213] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula IX
Figure imgf000046_0002
where Z is as set forth for formula I. [0214] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula IX
Figure imgf000047_0001
where X and Z are as set forth for formula I. [0215] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula IX
Figure imgf000047_0002
where m, n and Z are as set forth for formula I. [0216] The DMTD derivative of any previous paragraph, wherein the carboxylate comprises, consists essentially of, consists of a di-carboxylate. [0217] The DMTD derivative of any previous paragraph, wherein the carboxylate comprises, consists essentially of, consists of a tri-carboxylate. [0218] The DMTD derivative of paragraph 1, wherein the carboxylate is selected from ita- conate, citraconate, maleate, fumarate, mesaconate, where the carboxylates can be in the form of a salt with an alkali or alkaline earth metal, or an ester with an “R” group. [0219] The DMTD derivative of any previous paragraph, wherein the carboxylate does not comprise a (meth)acrylate wherein the ester group of the (meth)acrylate comprises, consists essen- tially of, consists of H or an R group. [0220] The DMTD derivative of any previous paragraph, wherein the substituent Y of the DMTD derivative of formula I comprises, consists essentially of, consists of “CH2CH[CH3 or H]C(O)OZ,” where “Z” can be X, RN+(R)3SO3-, RN+(R)3SO3-K+, “RSO3-Na+,” RSO3-NH4 +, “RSO3H,” or “RN+(R)3Cl-.” [0221] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000048_0001
where Z is X, RN+(R)3Cl-, RN+(R)3SO3-, RN+(R)3SO3-K+, RSO3-Na+, RSO3-NH4 +, or RSO3H. [0222] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000048_0002
where Z is RN+(R)3Cl-, RSO3-Na+, or RSO3H. [0223] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000048_0003
where Z is RN+(R)3Cl-, RSO3-Na+, or RSO3H. [0224] The DMTD derivative of any previous paragraph, wherein the reaction product com- prises, consists essentially of, consists of a compound of formula
Figure imgf000049_0001
where Z is RN+(R)3Cl-, RSO3-Na+, or RSO3H. [0225] A zwitterionic DMTD derivative comprising, consisting essentially of, consisting of the reaction product of: a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of i. a linear, branched, saturated or unsaturated, cyclic halogenated C1 to C22 alkyl or aryl quaternary ammonium group, ii. a quaternary ammonium containing halo-ether group, iii. a quaternary ammonium containing halo-alcohol group, iv. a quaternary ammonium containing epoxide group, v. a quaternary ammonium containing carboxylate group, and vi. a quaternary ammonium containing carboxamide group, and c. a strong base. [0226] The zwitterionic DMTD derivative of any previous paragraph wherein the reaction product comprises, consists essentially of, consists of a compound of for- mula
Figure imgf000049_0002
where R is as set forth in any previous paragraph. [0227] The zwitterionic DMTD derivative of any previous paragraph wherein the reaction product comprises, consists essentially of, consists of a compound of for- mula
Figure imgf000050_0001
where R and o are as set forth in any previous paragraph. [0228] The zwitterionic DMTD derivative of any previous paragraph wherein the reaction product comprises, consists essentially of, consists of a compound of for- mula
Figure imgf000050_0002
where R and p are as set forth in any previous paragraph. [0229] The zwitterionic DMTD derivative of any previous paragraph wherein the reaction product comprises, consists essentially of, consists of a compound of for- mula
Figure imgf000050_0003
where R is as set forth in any previous paragraph. [0230] A bis-DMTD derivative comprising, consisting essentially of, consisting of the reaction product of a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of i. a linear, branched, saturated or unsaturated, cyclic halo-alkyl or aryl group, ii. a (meth)acrylate group, and c. an oxidizing reagent. [0231] The bis-DMTD derivative of any previous paragraph wherein the reaction product comprises, consists essentially of, consists of a compound of formula
Figure imgf000051_0001
where “m” is 1, 2 or 3, and “n” is 2; and where “Y” is: “R,” a linear, branched, saturated or unsaturated, or cyclic C1 to C12, or C1 to C10, or C1 to C8, or even C1 to C6 alkyl or aryl group, or H; “CH2CH[CH3 or H]C(O)OZ,” where “Z” is H, or a C1 to C22 alkyl or aryl group. [0232] The bis-DMTD derivative of any previous paragraph wherein “m” is 1 and “n” is 2. [0233] The bis-DMTD derivative of any previous paragraph wherein “m” is 2 and “n” is 2. [0234] The bis-DMTD derivative of any previous paragraph wherein “m” is 3 and “n” is 2. [0235] The bis-DMTD derivative of any previous paragraph wherein “Y” is “R,” a linear, branched, saturated or unsaturated, or cyclic C1 to C12, or C1 to C10, or C1 to C8, or even C1 to C6 alkyl or aryl group. [0236] The bis-DMTD derivative of any previous paragraph wherein “Y” is H [0237] The bis-DMTD derivative of any previous paragraph wherein “Y” is “CH2CH[CH3 or H]C(O)OZ,” where “Z” is H, or a C1 to C22 alkyl or aryl group.

Claims

What is claimed is: 1. A DMTD derivative comprising, consisting essentially of, consisting of the reac- tion product of: a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of a: i. halo-ether group, ii. a halo-alcohol group, iii. an epoxide group, iv. a carboxamide group, v. a carboxylate group. 2. The DMTD derivative of any previous claim, wherein the reaction product comprises, consists essentially of, consists of a compound of formula I Formula I
Figure imgf000052_0001
where “X” is an alkali or alkaline earth metal, such as Li, Na, K, Mg, or Ca, a trial- kyl amine, or a quaternary amine, or H; “m” is 1, 2 or 3, and “n” is 1 or 2; and where “Y” is: “[RO]oR,” where “o” is an integer from 1 to 100; “R[OH]pA,” where “p” is an integer from 1 to 6 and “A” is H or an amine, such as a trialkyl amine or a quaternary amine salt; a carboxamide, such as a (meth)acrylamide of “CH2CH[CH3 or H]C(O)NHZ,” where “Z” is H, “R,” “RSO3-Na+,” “RSO3H,” or “RN+(R)3Cl-,” or a carboxylate, such as an itaconate, maleate, or, for example, a (meth)acrylate of “CH2CH[CH3 or H]C(O)OZ,” where “Z” can be X, RN+(R)3SO3-, RN+(R)3SO3-K+, “RSO3-Na+,” RSO3-NH4 +, “RSO3H,” or “RN+(R)3Cl-,” and where “R” is a linear, branched, saturated or unsaturated, or cyclic C1 to C12, or C1 to C10, or C1 to C8, or even C1 to C6 alkyl or aryl group, or H. 3. The DMTD derivative of any previous claim, wherein the reaction product further comprises, consists essentially of, consists of reaction with a base. 4. The DMTD derivative of any previous claim, wherein the reaction product further comprises, consists essentially of, consists of reaction with an oxidizing reagent. 5. The DMTD derivative of any previous claim, wherein the reaction product comprises, consists essentially of, consists of a compound of formula
Figure imgf000053_0001
where R, X, o, m and n are as set forth for formula I. 6. The DMTD derivative of any previous claim, wherein the reaction product comprises, consists essentially of, consists of a compound of formula
Figure imgf000053_0002
where X, m, n, p, and A are as set forth for formula I. 7. The DMTD derivative of any previous claim, wherein the reaction product comprises, consists essentially of, consists of a compound of formula IX
Figure imgf000054_0001
where X, m, n and Z are as set forth for formula I. 8. The DMTD derivative of any previous claim, wherein the reaction product comprises, consists essentially of, consists of a compound of formula
Figure imgf000054_0002
where Z is X, RN+(R)3Cl-, RN+(R)3SO3-, RN+(R)3SO3-K+, RSO3-Na+, RSO3-NH4 +, or RSO3H. 9. A zwitterionic DMTD derivative comprising, consisting essentially of, consisting of the reaction product of: a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of i. a linear, branched, saturated or unsaturated, cyclic halogenated C1 to C22 alkyl or aryl quaternary ammonium group, ii. a quaternary ammonium containing halo-ether group, iii. a quaternary ammonium containing halo-alcohol group, iv. a quaternary ammonium containing epoxide group, v. a quaternary ammonium containing carboxylate group, and vi. a quaternary ammonium containing carboxamide group, and c. a strong base. 10. A bis-DMTD derivative comprising, consisting essentially of, consisting of the reaction product of a. 2,5-dimercapto-1,3,4-thiadiazole (“DMTD”), and b. at least one of i. a linear, branched, saturated or unsaturated, cyclic halo-alkyl or aryl group, ii. a (meth)acrylate group, and c. an oxidizing reagent.
PCT/US2020/050947 2019-09-17 2020-09-16 2,5-dimercapto-1,3,4-thiadiazole ("dmtd") derivatives WO2021055388A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/760,830 US20220380326A1 (en) 2019-09-17 2020-09-16 2,5-dimercapto-1,3,4-thiadiazole (dmtd) derivatives
EP20780882.5A EP4031537A1 (en) 2019-09-17 2020-09-16 2,5-dimercapto-1,3,4-thiadiazole ("dmtd") derivatives
CA3150299A CA3150299A1 (en) 2019-09-17 2020-09-16 2,5-dimercapto-1,3,4-thiadiazole ("dmtd") derivatives
CN202080064720.8A CN114401949A (en) 2019-09-17 2020-09-16 2, 5-dimercapto-1, 3, 4-thiadiazole ('DMTD') derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962901312P 2019-09-17 2019-09-17
US62/901,312 2019-09-17

Publications (1)

Publication Number Publication Date
WO2021055388A1 true WO2021055388A1 (en) 2021-03-25

Family

ID=72659383

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2020/050947 WO2021055388A1 (en) 2019-09-17 2020-09-16 2,5-dimercapto-1,3,4-thiadiazole ("dmtd") derivatives

Country Status (5)

Country Link
US (1) US20220380326A1 (en)
EP (1) EP4031537A1 (en)
CN (1) CN114401949A (en)
CA (1) CA3150299A1 (en)
WO (1) WO2021055388A1 (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2736729A (en) 1953-08-20 1956-02-28 Basf Ag Substitution products of 1,3,4-thiadiazole and process
US3212892A (en) 1960-07-27 1965-10-19 Agfa Ag Preventing darkening and formation of precipitates in solutions of photographic developers
US4772546A (en) * 1985-10-16 1988-09-20 Fuji Photo Film Co., Ltd. Silver halide photographic material with high interimage effects
US5258395A (en) 1984-11-12 1993-11-02 Yamanouchi Pharmaceutical Co., Ltd. Thiazole compounds as inhibitors of SRS-A
US5414090A (en) * 1993-11-02 1995-05-09 Texaco Inc. Lubricant ashless antiwear-antioxidant additive
WO2001029155A2 (en) * 1999-10-20 2001-04-26 R.T. Vanderbilt Company, Inc. Thiadiazole additives and lubricating compositions containing the same
WO2001029156A2 (en) * 1999-10-20 2001-04-26 R.T. Vanderbilt Company, Inc. Thiadizole dimer additives and lubricating compositions containing the same
US20020058594A1 (en) * 1999-10-20 2002-05-16 R.T. Vanderbilt Company, Inc. Thiadiazole dimer additives and lubricating compositions containing the same
US20060168741A1 (en) * 2005-01-31 2006-08-03 Wilhelm Laufer Process for the production of Bis-DMTD
US20090156444A1 (en) * 2007-12-14 2009-06-18 R.T. Vanderbilt Company, Inc. Additive composition for ep greases with excellent antiwear and corrosion properties
JP2013234126A (en) 2012-05-02 2013-11-21 Fujifilm Corp Mercapto compound

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6211854A (en) * 1985-07-10 1987-01-20 Fuji Photo Film Co Ltd Silver halide color reversal photographic sensitive material
DE3684430D1 (en) * 1985-12-25 1992-04-23 Fuji Photo Film Co Ltd METHOD FOR PRODUCING AN IMAGE.
JPH05127295A (en) * 1991-11-06 1993-05-25 Fuji Photo Film Co Ltd Direct positive photographic sensitive material
JPH10148918A (en) * 1996-11-21 1998-06-02 Konica Corp Silver halide color photographic sensitive material
US7129031B2 (en) * 2003-06-19 2006-10-31 Agfa-Gevaert Radiographic silver halide photographic material having a good developing speed, an excellent image tone and low residual color after processing
CN102101691B (en) * 2009-12-18 2012-07-18 中国石油天然气股份有限公司 Preparation method of cerium oxide nanoparticles
CN106543099A (en) * 2016-10-30 2017-03-29 湖南工程学院 A kind of Biodegradable lube oil additive 2,5 dialkyl acetamides, 1,3,4 thiadiazoles and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2736729A (en) 1953-08-20 1956-02-28 Basf Ag Substitution products of 1,3,4-thiadiazole and process
US3212892A (en) 1960-07-27 1965-10-19 Agfa Ag Preventing darkening and formation of precipitates in solutions of photographic developers
US5258395A (en) 1984-11-12 1993-11-02 Yamanouchi Pharmaceutical Co., Ltd. Thiazole compounds as inhibitors of SRS-A
US4772546A (en) * 1985-10-16 1988-09-20 Fuji Photo Film Co., Ltd. Silver halide photographic material with high interimage effects
US5414090A (en) * 1993-11-02 1995-05-09 Texaco Inc. Lubricant ashless antiwear-antioxidant additive
WO2001029155A2 (en) * 1999-10-20 2001-04-26 R.T. Vanderbilt Company, Inc. Thiadiazole additives and lubricating compositions containing the same
WO2001029156A2 (en) * 1999-10-20 2001-04-26 R.T. Vanderbilt Company, Inc. Thiadizole dimer additives and lubricating compositions containing the same
US20020058594A1 (en) * 1999-10-20 2002-05-16 R.T. Vanderbilt Company, Inc. Thiadiazole dimer additives and lubricating compositions containing the same
US20060168741A1 (en) * 2005-01-31 2006-08-03 Wilhelm Laufer Process for the production of Bis-DMTD
US20090156444A1 (en) * 2007-12-14 2009-06-18 R.T. Vanderbilt Company, Inc. Additive composition for ep greases with excellent antiwear and corrosion properties
JP2013234126A (en) 2012-05-02 2013-11-21 Fujifilm Corp Mercapto compound

Also Published As

Publication number Publication date
CA3150299A1 (en) 2021-03-25
US20220380326A1 (en) 2022-12-01
CN114401949A (en) 2022-04-26
EP4031537A1 (en) 2022-07-27

Similar Documents

Publication Publication Date Title
US3932532A (en) Ethers of polyglycerol
US4650865A (en) Process for preparing tertiary ether amines
US11339123B2 (en) Alkoxylated secondary alcohol sulfates
GB1087413A (en) Improvements in or relating to amines
JPH0518623B2 (en)
WO2021055388A1 (en) 2,5-dimercapto-1,3,4-thiadiazole ("dmtd") derivatives
US4159277A (en) Zwitterionic compounds with a tetramethylene oxide moiety between the cationic and anionic charge centers
US2570503A (en) Process of preparing esters of aminesubstituted phosphonic acids
US3907815A (en) Process for preparing phosphorothioates and phenylphosphonothioates
JP4685006B2 (en) Method for producing bis (trimethylsilyloxy) silylalkylglycerol methacrylate
US4117237A (en) Unsymmetrical sulfosuccinate diesters
US3935243A (en) Method for preparing polyperoxydicarbonate esters
US4943664A (en) Surfactant products containing 1,3,4-butanetriol
CA3150294A1 (en) Redox flow battery electrolytes with 2,5-dimercapto-1,3,4-thiadiazole ("dmtd") and its derivatives
US5684182A (en) Sulfonated diphosphines and a process for their preparation
US4574061A (en) Alkoxy aryl sulfonate surfactants
US3013046A (en) Method for preparing a gasoline additive containing boron and phosphorus
SU729173A1 (en) Method of preparing glycidylic fluoroethers
CZ392798A3 (en) Process for preparing derivatives of phenoxypropionic acid
CN114181169B (en) Method for preparing N- (substituent) benzothiazine-4-ketone without participation of metal
US4578506A (en) Process for the preparation of tris(N-carbalkoxylaminomethyl)phosphine oxides and sulfides
JP2002003456A (en) Betaine-type monomer, method for producing the same and polymer thereof
EP0557462B1 (en) Method for producing ethanolamide alkoxylate
CA1117970A (en) Phosphorbetaines and process for making them
US2878272A (en) Acyl pentallkylguanidonium salts

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20780882

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 3150299

Country of ref document: CA

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020780882

Country of ref document: EP

Effective date: 20220419